JPS6035732A - Color photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent the color of a magenta color image from being made turbid and to improve the color reproducibility, color developing power and film strength by incorporating a specified polymer coupler latex forming a (co)polymer magenta color image into a silver halide emulsion layer. CONSTITUTION:A monomer capable of forming a dye by coupling with the oxidized product of aromatic primary amine as a developing agent is (co)polymerized, and the resulting polymer coupler latex forming a (co)polymer magenta color image is incorporated into a silver halide emulsion layer to obtain the desired color photographic sensitive material. Said monomer is represented by formula I , II or III (where R1 is H, 1-4C alower alkyl or Cl; each of R2, R3 and R4 is H or a substituent; A is -NHCO-, -OCO- or phenylene; B is alkylene, aralkylene or phenylene; X is H or a group which is eliminated by coupling; Y is -O-, -NH-, -S-, -SO- or the like; and each of m and n is 0 or 1), and for example, a monomer represented by formula IV or V is used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a novel magenta color image-forming polymer coupler latex capable of coupling with an oxidized product of an aromatic-grade amine developer. be.

・・The aromatic-class amine developer oxidized by color development after exposure of a silver halide color photographic material reacts with the coupler to produce indophenol, indoaniline, immethane, azomethine, phenoxazine, phenazine, and the like. It is known that pigments are produced and color images are formed. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used.

For example, acylacetanilide or benzoylmethane couplers are used to form yellow images.
Pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indacylon couplers are mainly used to form magenta color images, and cyan color images
In order to form an elephant, mainly phenolic couplers,
For example, phenols and naphthols are used.

Color couplers must meet various requirements, such as having good spectral properties and providing dye images that exhibit a high degree of long-term stability to light, temperature, and humidity upon color development. is necessary.

Incidentally, in multilayer color light-sensitive materials, it is necessary to fix each coupler in separate layers in order to reduce color mixture and improve color reproduction. There are many known methods for making this coupler anti-diffusion.

One method is to introduce a long chain aliphatic group into the coupler molecule to prevent diffusion.

Since the coupler produced by this method is immiscible with an aqueous gelatin solution, it is necessary to solubilize it in an alkali and add it to the aqueous gelatin solution, or to dissolve it in a high boiling point organic solvent and emulsify and disperse it in the aqueous gelatin solution.

Such color couplers may cause crystal precipitation in the emulsion, or if a high boiling point organic solvent is used, a large amount of gelatin is required to soften the emulsion layer, resulting in a thin emulsion layer ( The desire to do so has the opposite effect.

Another method of making couplers diffusion resistant is the use of polymeric coupler latexes obtained by polymerizing monomeric couplers.

Conventional methods for adding polymer couplers to hydrophilic colloid compositions in the form of latex include adding latex made by emulsion polymerization directly to gelatin silver halide emulsions, and adding lipophilic couplers to hydrophilic colloid compositions by polymerizing monomeric couplers. It is known to disperse polymer couplers in latex form in aqueous gelatin solutions. An example of the former emulsion polymerization method is the emulsion polymerization method in aqueous gelatin described in US Patent No. 3. J70. Rij,
In No. 2, an emulsion polymerization method in water was published by U.S. Pat.

, No. 2//. An example of the latter method of dispersion in the form of a lipophilic polymer coupler latex is given in U.S. Pat.
．． It is described in Ko 1/, Za 2θ issue.

The method of adding polymer couplers to hydrophilic colloid compositions in latex form has many advantages over other methods.

First, because the hydrophobic material is made into latex, the strength of the formed film does not deteriorate.Also, latex can contain a high concentration of monomeric coupler, so it is easy to emulse a high concentration of coupler. can be contained, and the increase in viscosity is small.

Furthermore, it has the advantage that there is no color mixing due to its non-migration property, and there is little precipitation of coupler in the emulsion film.

Among such polymer couplers, a magenta polymer coupler added in the form of a latex to a gelatin silver halide emulsion is disclosed in, for example, US Pat.

oro, xl1, british patent/, z4a7,611,
US Patent 3. Hirozi, toλ issue, same 3. Octopus T, Hiro 3
No. 6, West German Patent Co., 721. It is written in Jri No. 1, etc.

However, it is generally said that the absorption waveform of the magenta color image formed by the conventionally known magenta polymer coupler latex is rebroadened compared to the absorption waveform of the color image formed by the same type of magenta coupler that has not been polymerized, and therefore color reproducibility deteriorates. I had a problem. Well, it has been considered as a conventional method!・In magenta polymer coupler latex with pyrazolone core, ≠30n
There was unnecessary absorption of a yellow component near m, causing color turbidity.

By the way, the use of /H-(J,2.C)-8-pyrazolotriazoles as magenta couplers is described in U.S. Pat. It has drawbacks such as low solubility in solvents and relatively low coupling activity in ordinary developers. Therefore, in order to add the required amount in the form of an oil dispersion to a silver halide emulsion, the thickness of the emulsion layer must be increased, which often results in deterioration of sharpness.

The present applicant discovered imidazopyrazoles as a new magenta coupler that does not exhibit sub-absorption on the short wavelength side, has high color image fastness, and is easy to synthesize, and has filed a patent application (Japanese Patent Application Shojlf-23 (See Ko 3 Hiro issue).

Therefore, an object of the present invention is to first provide a novel magenta color image-forming polymer coupler latex in which the absorption waveform of the magenta color image formed is sharp and the color reproducibility is extremely excellent.

A second object of the present invention is to provide a novel magenta color image-forming polymer coupler latex which has extremely excellent color forming properties.

A third object of the present invention is to provide a new maze/red color image-forming polymer coupler latex which does not absorb unnecessary yellow components and gives a magenta color image without color turbidity.

An object of the present invention is to provide a color photographic material with strong film strength against blur.

The purpose of the present invention is No. 1! The objective is to provide a color photographic material with a thin film (improved sharpness) by polymerizing an imidazopyrazole-based magenta coupler.

In some aspects of the present invention, a polymer or copolymer having a repeating unit derived from a monomer represented by the following general formula [■], [■J or [■] having an imidazopyrazole core, or a magenta color image-forming polymer. This was achieved by incorporating coupler latex into a silver halogenide emulsion.

General formula (IJ R1) In the formula, R1 represents a hydrogen atom, an alkyl group having carbon number/~hiro, or t represents a chlorine atom, and R2, R3, and R4 are hydrogen atoms or substituents, e.g., each unsubstituted or substituted , alkyl group, aryl group, heterocyclic group composed of !-6 atoms, alkylamino group, acylamino group, anilino group, hydroxyl group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, alkylthio group, arylthio group, A represents a carbamoyl group, a sulfamoyl group, or a sulfonamide group; -NHCO-1-OCO-1 or a phenylene group, B represents an unsubstituted or substituted alkylene group, aralkylene group or phenylene group,
The alkylene group may be linear or branched. Y is 10-1-
NI-1-1-S-1-8O-1-8O2-1-CON
H-1-COO-, -NHCO-1 is 14N to I
C0N [represents -1-.

m and n represent m:=/'i when n2l, and m=o or l when n-O.

General formula [IJ, [■] and [North R2, R3, R4,
X and B will be explained in more detail. R2, R3, R4
is a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group (preferably one having 7 to 32 carbon atoms, for example, a methyl group, a propyl group, a butyl group, a trifluoromethyl group, a tridecyl group, a λ -methanesulfonylethyl group, 3-(3-pentadecylphenoxy)propyl group, 3-(pi-2-(Hiro-(Hiro-hydroxyphenylphenoxysulfonyl)phenoxy]dodecanamido)phenyl)propyl group, λ-ethoxytri Decyl group,
cyclopentyl group, J-(2, monoaminophenoxy)propyl group, etc.), aryl group (preferably one with 4 to 20 carbon atoms. For example, phenyl group, Hiro-t-
butylphenyl group, co.

q-di-t-amylphenyl group, hiro-methoxyphenyl group, etc.), heterocyclic groups (e.g., λ-furyl group, λ-chenyl group, λ-hirimicinyl group, λ-benzothiazolyl group, etc.), alkylamino groups (preferably is a carbon number group of C to C0. For example, an acetylamino group, propylamide group, benzamitono M, etc.), anilino group (e.g., phenylamino group, dichloroanilino group, etc.), an alkoxycarbonyl group (preferably a carbon number of 2 to 0). 20. For example, methoxycarbonyl group, phthoxycarbonyl group, ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (
Preferably one having a carbon number of λ to 20.

For example, acetyl group, butylcarbonyl group, cyclohexylcarbonyl Ti, etc.), arylcarbonyl group (preferably one with 7 to 20 carbon atoms. For example, benzoyl 4,
pt-butylbe/zoyl group, etc.), alkylthio groups (preferably those having 1 to 20 carbon atoms, such as methylthio group, octylthio group, niphenoxyethylthio group, etc.),
Arylthio group (preferably one with carbon number t-λθ, e.g. phenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.), carbamoyl group (preferably one with carbon number/~20, e.g. heethyl lupamoyl group) ,
N, N-dibutylcarbamoyl group, N-methyl-N-i
tylcarbamoyl S, etc.>, sulfamoyl group (preferably up to 20 carbon atoms; for example, N-ethylsulfamoyl group, N, N-S-f-A/sulfamoyl group, N
, N-dipropylsulfamoyl group, etc.) or sulfonamide i (preferably one with carbon number i, -, zoO; for example, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfo/amide group, etc.).

X is a hydrogen atom, a /-rogen atom (e.g., chlorine atom, bromine atom, etc.), a cup-1 nong leaving group connected by an oxygen atom (e.g., acetoxy group, pro/1!noyloxy group, benzoyloxy group, etoyasioxaloyl group) Oxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, Hiro-cyanophenokyl group, Hiro-Titans J lephonamide phenoxy group, α-naphthoxy group, gucyanoxyl group, Hiro-methanesulfonamide -phenoxy group, α
-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethoxy group, benzyloxy group, λ-phenethyloxy group, λ-phenoxyethoxy group,! -phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.)
, campling leaving groups linked via a nitrogen atom (for example, those described in Japanese Patent Application No. 331, No. 331, specifically, benzenesulfonamide group, N-ethyltoluenesulforamide group, heptafluoro Butanamide i!
, Jl Hiro, Yu, 6- is antafluorobenzamide group, octane sulforamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, l-P: IJ #4N -t # j -dimethyl-λ, ≠-
Dioxo 3-oxazolidinyl L /-benzyl-j
-ethoxy-3-hydantoynyl group, cooxy/,
2-dihydro-l-pyridinyl group, imidazolyl group, pyrazolyl group, 31j-diethyl-7,co, hiro-triazol-l-yl group,! - or 6-promobenzotriazol-/-yl group, j-methyl-7,2゜3, Hiro-
triazol-1-yl group, benzimidazolyl group, etc.)
, a coupling-off group linked via a sulfur atom (e.g. phenylthio group, cocarpoxyphenylthio group, -1methoxy!-octylphenylthio group, ≠-methanesulfonylphenylthio group, Hiro-octanesulfonamidophenylthio group, benzylthio group) group, cone'anoethylthio group, j-phenyl-λ, 3,4L, yo-tetrazolylthio group, 2-benzothiazolyl group, etc.).

B represents an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group having 7 to 70 carbon atoms;
The alkylene group may be linear or branched. Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, k
Examples of tamethylene, hexamethylene, tetramethylene, and aralkylene groups include benzylidene and phenylene groups such as p-phenylene, m-phenylene, and methylphenylene.

Examples of substituents for the alkylene group, aralkylene group, or phenylene group represented by fcB include aryl groups (e.g. phenyl group, ditro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group, etc.), aryloxy group) (e.g., phenoxy group, etc.), acyloxy group (e.g., acetoxy group, etc.), acylamino group (e.g., acetylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, etc.), Halogen atoms (e.g. evaporative fluorine atoms,
chlorine atom, bromine atom, etc.), carboxy group, carbamoyl group (PJt, methylcarbamoyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), sulfonyl group (e.g., methylsulfonyl group, etc.). When there are two or more, they may be the same or different.

In the general formulas (IJ, (IIJ, and [111)) of the present invention, the hydrogen atom or R1 is particularly preferably a lower alkyl group (particularly a methyl group), and R2, R3, and R4 are hydrogen atoms or each unsubstituted or substituted. An alkyl group or an aryl group is particularly preferable, and X is particularly preferably a hydrogen atom, a rogen atom, or a coupling-off group connected by a nitrogen atom, and when n=/, Y is -
N HCO- is particularly preferred, B when m=/ is particularly preferably an unsubstituted alkylene group, aralkylene group or phenylene group, and A is particularly preferably -NHCO-.

Next, preferred specific examples of the monomeric couplers of the general formulas CD, (IIJ, and mark ■) of the present invention will be given.

C-co CH3 ■ -3CH3 C-gu CH3 -tcH3 C-4Cl-13 1 C-/+2 H3 H3 C-/Hiroshi C[■3 H C-/j e C-/A CH3 ■ C-/ ZaC -7riC-2°C-', 2/ -23 The above general formula CIJ, (IIJ and [Kita's monomer coupler is expressed in Japanese Patent Application Shoj Zaichi 23≠3hiro No. 3 or J, Heterocyclic Chem, Volume 10, 4
It can be synthesized by reacting an amine derivative of imitazopyrazole obtained by the method described on page 1// (1973) with an acid chloride having a vinyl group.

Monomer production example 6 - Synthesis of methyl-3-(3-(3-methacrylamido)-propyl J-/H-imidazo(/,,2-bJ-pyrazole (C-t)) Reaction scheme Intermediate 2 Intermediate 3 (1) Synthesis of Intermediate 4 Hiro-(Hiro-nitrophenyl)butyric acid is used as a raw material, converted to acid chloride with thionyl chloride, and processed by Rosenmund reduction to <z-(p-nitrophenyl)butyral (Intermediate 1
) was obtained.

Mix 7 g of medium weight male, g of acetic anhydride and powdered potassium acetate, male y, oil bath temperature/! 0-/gθ0
The mixture was heated at C for 2 hours, cooled, poured into ice water, and stirred for 72 hours.

The oil was roasted and dissolved in 100 ml of carbon tetrachloride.

Bromine was gradually added dropwise while stirring at room temperature. While the bromination reaction progresses at the same time as the dropwise addition, the color of bromine disappears, but as the reaction approaches the end point, the dropwise addition is stopped at the point where the color no longer disappears (bromine, about 7!rji), and the reactant is added to 3oOml. of methanol and left at room temperature for 1 day. Thereafter, the solvent was removed, and the residue was separated on a silica gel flash column to obtain the oily intermediate (C-1, 6.!1iI (rO,
A% yield) was obtained.

Intermediate 27, jy and anhydrous hydrazide/AOg θθd
was dissolved in anhydrous ethanol and heated to reflux for 75 hours under a nitrogen stream, the solvent was removed, and the residue was refluxed with ether.
oml, anhydrous potassium carbonate/00ji was further added, and the mixture was stirred at room temperature for 2 hours.

After filtering and concentrating the furnace liquid, 63% of the oily intermediate 3 was obtained. ry obtained.

Without purifying intermediate 3, intermediate 3j3.1/i
and 3-aminocrotononitrile l♂y, 200ml
The solution was dissolved in ethanol and heated under reflux for 30 hours under a nitrogen stream. Thereafter, 200 ml of ethanol was further added, 200 ml of 20% sulfuric acid was added, and the mixture was heated under reflux on an oil bath for 2 hours. After the reaction was completed, solid sodium hydrogen carbonate was added little by little while paying attention to the reaction solution to neutralize the solution.

After filtration, the solid was washed three times with ethanol, and the washings and filtrate were combined and concentrated to dryness. Inorganic substances and starting components were removed through a silica gel shot column to obtain 22.7 g of Intermediate 4 as a colorless powder.

(2) Synthetic intermediate 4 of compound (C-t). 27. O,! /(0,1m01) in acetonitrile 2jOml, pyridine/1mA! , methacrylic acid chloride mixed with nitrobenzene/ml.

Slowly drop jjjj (0, / 0! mol),
After a stirring reaction/hour at 100C or less, water and ethyl acetate were added and an extraction operation was performed. After drying the ethyl acetate layer, the solvent was removed and recrystallized with acetonitrile to obtain C-1.2.
0.2g was obtained.

Elemental analysis (C19H22N40) (theoretical value) C near (:1.7+1'% H:g, Ig
%N: I7.31 section (experimental value) C: qO, 70% H: X, jij%N: /
7. ．． 2/T Other monomeric couplers can also be synthesized according to the above method.

The polymer coupler latex of the present invention has the general formula [■]
It may be a homopolymer of monomeric couplers of the general formula (IJ, [:nJ, ([IJJ(, general formula CI), (I[J and/or [biliary monomeric couplers and non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developing agents). In any of the above cases, two or more types of monomeric couplers included in the general formula CD may be used as the monomeric couplers of the general formula (IJ), and similarly, in the general formula [IIJ or [l] As a monomeric coupler, the general formula [I
[J or two or more types of units included in [1■] may use physical strength pullers.

Among the above, a copolymer of a monomeric coupler of the general formula (I) or (Ill) and a non-color-forming ethylene-like monomer described below is preferred.

Next, non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-class amine phenomena include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (
methacrylic acid, etc.), esters or amides derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, 1-butylacrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, 1so-butyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and β-hydroxy methacrylate), vinyl esters ([Jt vinyl acetate, vinyl propionate and vinyl laurate), acrylate to methacrylate, vinyl aromatic compounds (e.g. styrene and its derivatives, e.g. vinyl toluene, divinylbenzene, vinyl acetophenone and sulfostyrene)
, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (e.g. ethyl ether), maleic acid ester, N-vinyl-λ
-pyrrolidone, N-vinylpyridine, and λ- and ≠-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the general formula (IJ
, OfJ, (The ethylenically unsaturated monomer for copolymerization with the monomeric coupler corresponding to IJ is determined by the physical and/or chemical properties of the copolymer formed, e.g. solubility, photographic colloidal composition. The binder can be selected such that its compatibility with, for example, gelatin, its stability, thermal stability, etc. are favorably influenced.

The magenta polymer coupler latex used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerizing a monomer coupler in an organic solvent and dispersing it in an aqueous gelatin solution in the form of a latex, as described above. Alternatively, it may be produced by direct emulsion polymerization.

A method of emulsifying and dispersing a lipophilic polymer coupler in an aqueous gelatin solution in the form of a latex is described in US Patent No. 3. ≠!
/, No. 1.20, Teha U.S. Patent II on Emulsion Polymerization
-, 010. ．． The method described in No. 2//, No. 3,370, No. 52 can be used.

The synthesis of the magenta polymer coupler of the present invention includes a polymerization initiator,
As a polymerization solvent, JP-A-Shojt-! tjl13, JP-A-Shoj7
-Tage7ta11 JP-A Showj7-/7t031, JP-A-Showj7
-201103g, JP-A Showa 5t-21f711r, JP-A Showa! l-107311 Tokukai Sho! r-g20≠Hiroshi, special request! 7-22t is carried out using the compound described in 3.

The polymerization temperature must be set in relation to the molecular song of the polymer to be produced, the type of initiator, etc.
Although it is possible to reach 0C or higher] Huh? 3 o'c ~ 100
Polymerizes in the 0C range.

General formula CD, ([J, (
[The ratio of the colored portion corresponding to lIJ is normally desirably S to go% by weight, but is preferably 20 to 70M in terms of color reproducibility, color development and stability. In this case, the molecular bone (
The number of grams of polymer (containing 1 mole of monomeric coupler) ranges from about 250 to 200, but is not limited thereto.

A manufacturing method example of a polymer coupler is shown below (Manufacturing method ■) Manufacturing method example (2) 2-Methyl-3-(J-(j-methacrylamido)-propyl]-/H-imidazoC1,2-bJ-pyrazole (C , t) and butyl acrylate (lipophilic polymer Cassilar (I)) Monomer coupler (c-j), zog, butyl acrylate, 20 g, dioxane, 2 ooml of a mixture of nitrogen After heating to RO0C with stirring in a stream of air, dioxane 2Qme containing dimethyl azobisisobutyrate o,sg was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled and diluted with water/
, jl, and the precipitated solid was separated and washed thoroughly with water.

By heating and drying this solid under reduced pressure, 3g of lipophilic polymer (I) can be obtained! I got 9.

Chlorine analysis of this polymer coupler showed that the copolymer formed contained a jO0r monomeric coupler (C-j).

Next, a method for dispersing the lipophilic polymer coupler (ILr-gelatin in the form of latex in the aqueous layer) will be described. First, two solutions (a) and (b) are prepared as follows.
I arranged it.

a) Heat a 30% by weight aqueous solution of bone gelatin (pH 4 at 0C, 2009) to 3♂0C and add a 10% by weight aqueous solution/Aml of sodium lauryl sulfate.

b) 20g of the above lipophilic polymer coupler (i)
♂Dissolve 200ml of ethyl acetate (C) at 0C.

Next, solution (1) was put into an explosion-proof mixer that was being stirred at high speed, and solution (a) was rapidly added thereto and stirred for 7 minutes, then mixing 1 was stopped and ethyl acetate was removed by distillation under reduced pressure. Excluded. A latex (T') was thus prepared by dispersing the lipophilic polymer coupler in a dilute gelatin solution.

Manufacturing method example (3) 6-methyl-3-methacrylamide/H-imidazo-
[/,,2-1) Copolymer coupler of J-pyrazole (C-,2) and butyl acrylate (oleophilic polymer coupler (■n) Monomer coupler (cr), 2og, butyl acrylate, 20g A mixture of 200 yrtl! of methyl cellosolve was heated to OoC under stirring in a nitrogen stream, and then 20 ml of methyl cellosolve containing dimethyl azobisino-'iδ acid θ and I was added to initiate polymerization. After reacting for 5 hours, the reaction mixture The mixture was cooled and poured into water i and sl, and the precipitated solid was separated and washed thoroughly with water.

By heating and drying this solid under reduced pressure, 32.0 g of a lipophilic polymer (1■) was obtained2. This polymer coupler was determined by chlorine analysis to be a monomer coupler (C --2) was shown to be contained.

Next, a method for dispersing a lipophilic polymer coupler (Ji) in an aqueous gelatin solution in the form of latex will be described. First, solutions of two zelkovas (a) and (b) were prepared as follows.

a) Heat 200 g of a 30% by weight aqueous solution of bone gelatin (pH f, t at 3!0 C) for 3r 0 CVCm and add 76% by weight of an IO solution of sodium lauryl sulfate in water.

b) The above lipophilic polymer coupler (2θ)
Dissolve in 200 ml of ethyl acetate at C.

Next, the solution (b) was put into an explosion-proof mixer that was being stirred at high speed, and the solution (at) was rapidly added thereto and stirred for 7 minutes, then the mixer was stopped, and ethyl acetate was removed by distillation under reduced pressure. The lipophilic polymer coupler was thus dispersed in a dilute gelatin solution to form a latex.

Next, the following lipophilic polymer coupler was prepared in the same manner as in Production Example λ, 3 (Production Method ■).

The dispersion of these lipophilic polymer couplers is also carried out in the above production example (
21, it can be dispersed in latex similarly to (3).

(Production method [) Production method example (18) 6-methyl-3-acrylamide-/H-imidazo-(
/,,i! Copolymer latex of copolymer latex of bJ-pyrazole (C-/) and butyl acrylate methacrylic acid (containing oleyl methyl tauride lI in a flask of polymer latex coupler (At) 31/, 21 J of an aqueous solution was stirred and passed through a nitrogen stream. After adding 2% aqueous ti/!ml of potassium persulfate to the aqueous solution, the monomer coupler (C-/), 201/, butyl acrylate/rg, and methacrylic acid rg were added in methanol 30
A solution heated and dissolved at 0 ml of VC was added dropwise over 20 minutes.

/hour reaction regression 2% aqueous solution of potassium sulfate was added. After reacting for another hour, methanol and water were distilled off.

After cooling the formed latex, pH the latex solution with N sodium hydroxide! :, O and filtered once.

The polymer concentration of the formed latex was F, J'%, and nitrogen analysis showed ≠r in the polymer. It was shown that 7 monomeric couplers (C-/) were contained.

Next, the following copolymer coupler latex was prepared in the same manner as in Production Example 1 (Production Process ■).

The magenta polymer coupler latex of the present invention can be used alone or in combination of 21 or more.

The magenta polymer coupler latex of the present invention is disclosed in US Pat.
．． 1. It can also be used in combination with the magenta polymer coupler latex described in If and the like.

The magenta polymer coupler latex of the present invention may also be combined with a hydrophobic magenta coloring coupler, such as U.S. Pat. toy issue, 3,012, 1. - issue 3, 31/27, 21 issue,
Same J, 3//, No. 1776, Same 3, ≠l, 3, No. 1,
Same s, ziy, ttt kota, same 3. ! rl, issue 3/9, same 3. -+I2,322, 3. t/j,! 0/,
No. 3, 13'l, 9o, r, 3. guri/
, No. 1, West German patent/.

? io, ≠6, West German patent application (OLS) 2.

Goor, tt! Issue, same λ, Hiro 77, ri≠! No., same λ, ≠
ig, rijri issue, same co, ≠2≠, ≠67 issue, equity tl'
0-/; o s No. 7, JP-A-Sho J-/-2012 No., same! λ-j♂ri No. 22, same≠2-/2ri No. 13g,
Doko Turf No. 17027, same! ro-isri No. 334,
same! 2-Hiroshi, 2/, 2/ issue, Geta-7≠021 issue, 1O-t0233 issue, same j/-2 Otsu! 1Lt No. 1, same!
The magenta coupler described in No. 3-43/22, etc. is allowed in the United States! , 2t9. /j za issue, same λ, 27 no, li 7
No. 2.30tI.

Rihiro θ, 2,3//, 020, +2. J, 22
．． 0.27, 2.3tO, 2Ir9, 2゜77
2.113, same x, roi, i7o, same λ, 0/
, / 7/, same J, /, IP, 15i16, British patent i, irl, rri no. 0, German patent /, /4'J,
A dispersion dispersed in a hydrophilic colloid by the method described in No. 707 etc. can be impregnated (loaded) by the method described in JP-A-KOKAI SHOYU/-3RI 1 #3 and used. A hydrophobic magenta coupler is added to the magenta polymer coupler latex of the present invention using a Japanese Patent Application Laid-open No.
It can also be impregnated (loaded) and used by the method described in U.S. Pat. Here, impregnation (loading) refers to hydrophobic magenta
A state in which the coupler is contained within magenta polymer coupler latex, or a magenta coupler
This means that it is deposited on the latex surface. However, the exact mechanism by which impregnation (loading) occurs is not known.

The magenta polymer coupler latex of the present invention was developed in U.S. Pat.
, /gut, 01t2, 3,227, Yujhiro, 3.733.20/, 3LA/7. Jri No. 7, No. 3
, No. 703.37jf, 3.1. /j, jOt issue, same 3. ．． 2t o, SO6, same 3, t20.7#! issue,
Same 3. Otsu 3.2.3 Hiroj-No. 3. Za6ri, 2ri No. 1, 3. t'12. ≠Ijt No. 3,770,113
1. No., same, 3. IOJ ≠ j issue, British patent/, 20/
, //θ issue, same/.

Development inhibitor release (DI
R) Coupler wo U.S. special p2, 2Ay, i! No., same, 2
, 272, 191, 2.30'l.

Rihiro θ, 2,3//, 020, λ, 32λ,
No. 027, No. 2,31yO, No. 21, same.

υ-, No. 163, same 2. r01. /”70@, same λ, ♂
0/, /7/, 3.6/ri, /ri no.5, British patent/
,/Kl,! ;90, German patent 1. /1/-3,70
It is also possible to use a dispersion dispersed in a hydrophilic colloid by the method described in JP-A No. 3/-391!3, etc., or by impregnating the dispersion with a hydrophilic colloid by the method described in JP-A-3/-391!3. It can also be used by impregnating magenta polymer coupler latex with the method described in JP-A-5I-S7 Rihiro 2, J-Hiro-3, 2, J, T2, U.S. Patent No. 1, Tata, 3T3, etc. You can do that too.

Also published in Germany, λ, jf2ri, No. 360, λ, Hirogu♂,
OA No.3, same, (,1o, z≠ No., U.S. Patent 3.ri21,0g/no., same3.ri!♂, Tata No.3, same3.ri4
/, Tatata, Dohiro, 04+! 9.

4#! ; No., same≠, 0!2. ．． 2/3 No. 3.37, j, No. 22, No. 3. θ≠3. Ari No. 0, 3゜3AI
I-, No. 02, 2, 31.2 7. Hirohiro! No. 3.
21r7. It is also possible to use the DIR compounds described in, for example, No. 29, Vol.

The magenta polymer coupler latex of the present invention is also disclosed in US Pat. No. 46, West German Patent Co., o.
2+, IIT issue, JP-A-Sho≠2-/, 23A2! Issue, same Kota/3/1 issue, same jλ−≠! Colored Magenta fJ-' Sea 1 U.S. Patent No. 3.
Za7A, ≠2za issue, same 3゜! rgO, 7λ2, the same,
Tataza, 3/Hirogo, same, ZaOg, 3.2ri, same 2.
7≠2.132, Jf7.723, etc., and the competitive couplers described in U.S. Patent No. 2,331. ．． No. 327, same, 72t, tsri No., same, j3t, No. 3.27,
Same.

03.7.2/issue, same, 70/, /27, same 3
．． 700, 'Aj No. 3, etc., stain inhibitors,
British patent/, 32t, f-zari number, US patent 3゜4t
, No. 32,300, 3. t2g, riOrigo, same 3, j
7 Hiro, No. 627, J, j7.3.030, No. 3.
It can also be used in combination with the dye image stabilizer described in No. 7z≠, No. 337, etc.

Commonly known couplers other than maze/liquid forming couplers can be used in making the color donor adhesive materials using the present invention. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a pallast group in its molecule. The coupler may be either di-equivalent or di-equivalent to silver ion.

It may also include a colored coupler that has a color correction effect, or a coupler that releases an image suppressor along with the phenomenon.The coupler may be a coupler in which the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat. ,j
Ot issue, same 3, t, tos', 1y4A issue, same 3.13
/, No. 113, J, No. 312.3.22, J
, 7.2j, No. 072, 3, 1rl, Doug! No., West German Patent/, j≠71rtr, West German Application Co., 2/Ri, Ri No. 77, Same Co.

26/, 36/ issue, same λ, Hirohiro, oot issue, British Patent/, Hiro, 2j, issue 020, special public Akira! ;/-10713
No., Japanese Patent Publication No. 7-21. /No.33, Dohiro? -73/Hiroshi 7
Same issue! /-10,2 Otsu 3 No., same t.

-63≠/issue, same! 0-/, 233 Hiro 2, Sameta O-/
30 Hiro≠λ, same! /-, 2/za 27, same jO-47
This is written in the tjO issue etc.

Phenol compounds, naphthol compounds, etc. can be used as the 7-A color coupler. Specific examples are US Patent λ, 36 Ri, Ri 2? No., same λ, ≠3≠, 27
No. 2, same λ, ≠7≠, λ 3, same 2. j, l/, 1
No. 01, same 2. lf? j, No. 1.26, Hiroshi 3,03,
Zari No. 2, No. 3, 3//.

Hiroshi No. 76, same 3. Hiroshi Jl, 3/j issue, same 3. ≠7 otsu,!
No. 63, 3. j♂3. ri No. 71, 3゜jY/, 3
No. 13, 3,767, (1// issue, Dohiro, 0OIA,
riλri issue, West German patent application, ≠lhiro.

Za No. 30, same 2. HirojlLL, No. 322, JP Akihiro g-
45F131, J/-2t03'1, tiej
tO! T,! R issue, same! /-1lAt12g issue, same! !
-730jtO.

Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in two or more different layers.

In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as those described in U.S. Pat. - Mixed with silver halogenide emulsion.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The silver halogenide emulsion used in the present invention contains not only silver chloride and silver bromide but also silver chloride, such as silver chlorobromide,
It consists of silver iodobromide, silver chloroiodobromide, etc., and is finely dispersed in a hydrophilic polymer such as gelatin. Depending on the intended use of the photosensitive material, those having a wide range of dispersed average particle size ranging from about 0.1 micron to about 3 micron are selected. Furthermore, these silver halide emulsions may be chemically sensitized such as sulfur sensitization, gold sensitization, or reduction sensitization, and may contain sensitivity-enhancing agents such as polyoxyethylene compounds and onium compounds. It's okay.

Not only emulsions of the type in which a fc latent image is mainly formed on the surface, but also emulsions of the internal latent image type in which the latent image is formed inside the grains can be used in the present invention. Furthermore, two or more kinds of separately formed silver halide photographic emulsions may be mixed.

The hydrophilic polymer material constituting the photosensitive layer of the present invention includes:
Proteins such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, polymeric non-electrolytes such as polyacrylamide, acidic polymeric substances such as alginate and polyacrylate, polyacrylamide treated by Hoffmann rearrangement reaction, acrylic acid and N-vinylimidazole. Polyampholytes such as copolymers of US, 4', λir, i
The crosslinkable polymers described in yj are suitable. Further, the hydrophilic polymeric substance forming the continuous phase may contain a dispersed hydrophobic polymeric substance, for example, a latex such as butyl polyacrylate.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material.

Those compounds are ≠-Hydroxy-O-methyl-/, 3
, 3a, 7-titrazaindene, 3-methy/l/penzthiazole, /-phenyl-termercaptotetrazole, as well as many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. is known since ancient times.

An example of a compound that can be used is “Re5earchDi”
5closure''/7.g4'J(/97.1
' / July issue) Page 24 ■ Antifoggan
The original literature is listed in the section d and Stabilzer.

Surfactants may be added alone or in combination to the photographic emulsion of the present invention. Although they are used as coating aids, they are sometimes also applied for other purposes, such as emulsification dispersion, sensitization, antistatic, antiadhesion, etc.

These surfactants include natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide type, glycerin type, and grindol type, higher alkyl amines,
Boke-grade ammonium, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carbonic acid, sulfonic acid, phosphoric acid, sulfate ester groups, phosphate ester groups, amino acids, aminosulfones, sulfuric acid or phosphoric acid of amino alcohols It is divided into amphoteric active agents such as esters.

Spectral sensitivity and superchromatic sensitization can be achieved in photographic emulsions by using cyanine dyes such as cyanine, merocyanine, and carboxy/anine alone or in combination, or in combination with styryl dyes and the like.

These color sensitization techniques have been known for a long time and have been published in the US patents λ, gr, s≠! No., λ, P/, 2゜322, No. 3,397. OtO issue, 3,1/! , No. 633, 3
．． 62g, Riotugu issue, British patent/,/ri,! , No. 302, same/ , 24L, 2, ! 18” issue, same/1.2
3. No. 42, West German Patent Publication No. 2.030, 32, same, /, 2/, No. 710, Special Publication Show≠3-Ko 23
It is also described in No. 2, Gugu/Re, No. 030, etc.

The selection depends on the wavelength range to be sensitized, the purpose of the photosensitive material such as sensitivity, etc.
It can be arbitrarily determined depending on the purpose.

The hydrophilic colloid layer, especially the gelatin layer, of the photosensitive material used in the present invention can be hardened with various crosslinking agents. For example, inorganic compounds such as chromium salts and zirconium salts; mucochloric acid and aldehyde compounds such as λ-phenoxy-3-chloromarealdehyde acid described in No. I'72; Compounds having a plurality of single epoxy rings, which are useful in the present invention, are described in Japanese Patent Publication No. 3 Ko-7,133;
7-♂, poly-(/-aziridinyl) compounds described in 7-O, as well as U.S. Patent No. 3,3t2, r27,
3,3 Kota, active halogen compound described in 2g7, US Patent λ, 5i'F.

1t/issue, same 3. j♂λ, No. 32.2, Belgian Patent No. Aff4. A non-aldehyde crosslinking agent such as a vinyl sulfone compound known as Guhiro θ is particularly suitable for use in the photosensitive material used in the present invention.

The silver halide photographic emulsions of this invention are often placed on a support. As the support, hard materials such as glass, metal, or ceramics, or other flexible materials may be used depending on the purpose. Typical examples of flexible supports include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, and laminates thereof, and baryta or α-olefin. Papers coated with polymers, in particular polyethylene, polypropylene, ethylene-butene copolymers, etc., and plastic films with a roughened surface, such as those shown in Akihiro Shibu 7-/R, 01g, are also advantageously used. Depending on the purpose of the photosensitive material, these supports may be transparent, colored by adding dyes or pigments, made opaque by adding titanium white, etc., or made opaque by adding CV, carbon black, etc. You can choose from those with light-shielding properties.

Each layer of the photographic material may be coated by dip coating, air knife coating, curtain coating, or US patent λ, t♂/,
It can be coated by various coating methods including extrusion coating using hopper f described in No. 22-22. If necessary, US patent 2.7t/, 7? / issue, same 3,301° tag No. 7 and same, ri≠/, rye issue, same 3. ! 21,! It is also possible to apply layers of up to λ or more at the same time by the method described in eg No. 21r.

The light-sensitive material of the present invention can also be used in a so-called multilayer construction type in which emulsion layers with different color sensitivity and color development are layered and coated on a support. This can also be realized in a so-called mixed packet JJ1, which is a type in which emulsions with different properties are mixed and coated on a support. The photosensitive material of the present invention can be realized in various forms. Examples include color negative film, color positive film, color reversal film, color photographic paper, and color reversal photographic paper.

In order to obtain a dye image of the color photographic material of the present invention,
After exposure, development processing is required. The development process basically includes color development; bleaching; and fixing steps. In this case, each step may be independent, or two or more of the steps may be performed using processing liquids having those functions, and the processing may be completed in one cycle. Further, each step can be divided into two or more times as necessary. In addition to the above, the development process includes pre-hardening, neutralization, first development (black and white development), stabilization, water washing and other processes, which may be combined as necessary. The processing temperature is set within a preferable range depending on the photosensitive material and the processing recipe, but is generally set between 0C and 0C. Note that it is not necessary that the set temperature for each step in the series of processing be the same.

The color developing solution is an alkaline aqueous solution containing a compound, i.e., a developing agent, whose oxidized product reacts with a color former called a coupler to form a color product, with a pH of J''-r or higher, preferably 2 to 7.2. The developing agent refers to a compound having a primary amine group on an aromatic ring and capable of developing exposed silver halide, or a precursor for forming such a compound.

For example, Hiro-amino-N, N diethyla = IJ 7.
3-Methyl-Hiro-amino-N,N-diethylaniline,
≠-amino-N-ethyl-N-β-human Cl xyethylaniline, 3-methyl-guamino-N-ethyl-N-
β-hydroxyethylaniline Hiromino-3-methyl-N-ethyl-N-β-methanesulfamide ethylaniline, μm amino-N,N-dimethylaniline, Hiro-amino-3-methoxy-N,N-diethylaniline , Guamino-3-methyl-N-ethyl-he-β-ethoxyethylaniline, Hiro-amino-3-methoxy-N-ethyl-he-β-methoxyethylaniline, Hiro-amino-3-
β-memetasulfoadoethyl-N,N-diethylaniline and its salts (e.g. sulfate, hydrochloride, sulfite, p
-) luenesulfonate, etc.) are listed as preferred representative examples. Other U.S. Patent No. λ,/3. oiz
Same number! Octopus, No. 374, Tokukai Akihiro f-A Hiro 7
No. 33 or by F. A. Mason, Photogr.
abicProcessing Chemistry
(FocalPress-London edition/published in 2013), page 22, 1222T, written by H-James “Tb
e Tbeory of the Photograpb
ic, Process” (Macmi 11 an
* New York edition (/ri77) pp3/
It is also written in J--320 etc.

Also Tbe Theory of the Photo
graphicProcess' (1st edition) p p
! Aminophenols described in / / -3/j etc. may be used.

Furthermore, combined use with 3-pyrazolidones is also possible.

Various additives can be added to the color development liquid as required. Typical examples include alkaline agents (e.g. alkali metal and ammonium hydroxides, carbonates and phosphates), pH adjusting or buffering agents (e.g. weak acids and bases such as acetic acid and boric acid, and their salts). , development accelerators (e.g. U.S. Patent λ).

Various pyridinium compounds and cationic compounds described in tttttr, to hiro issue, 3.67/, aμ 7, etc., potassium nitrate and nitrate) 2. J'77゜/, 27
Polyethylene glycol condensates and derivatives thereof, such as those described in British Patent No. 020.033 and Tata No. 020.033, Tata No. 7C, etc.

Nonionic compounds such as polythioethers as typified by the compounds described in No. 02θ, No. 032, US Patent No. 3,07. 027, other organic amines such as pyridine and ethanolamine, benzyl alcohol, hydrazine, etc.), antifoggants (
For example, alkali bromide, alkali iodide, US patent λ,
Hiro t, y Hiro O, same, 6ta 4. ．． Including the nitropenzimidazoles described in No. 27/, mercaptobenzimidazole, j-methylbenttriazole, /-
Phenyl! -Mercaptotetrazole, U.S. Patent J,
//3. Zat≠No.3, 3≠2. ! No. 24, 3. ．．
2F! , No. 9?6, No. 3°t/j, No. 3.22, No. 3.
7. / Compounds for rapid processing described in No. 772゜2//, thiosulfonyl compounds described in British Patent No. 772゜2//, or unafenadine N oxide as described in No. 7 etc., and other fog suppressants described in Scientific Photographic Handbook, Vol. Ill.

j/No. 3, same 3. //, /,! /Hiroshi No., British patent l.

No. 030, '14-, Ibid/, /'Au, IAII, IAII, Ibid/, λj/, jtj1, and the stain or sludge inhibitor described in US Pat. Ta36. Multi-layer effect accelerators and preservatives known as Hiro No. 7, etc. (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide additives, etc.)
There is.

The color photographic material of the present invention can also be subjected to a step prior to color development.

The first developer for color reversal film is also a step prior to color development, and an alkaline aqueous solution containing one or more developing agents such as hydroquinone, l-phenyl-3-pyrazolidone, and N-methyl-p-aminophenol is used. and
In addition, inorganic salts such as sodium sulfate, pH adjusters and buffers such as borax, boric acid, sodium hydroxide, and sodium carbonate, alkaline rogens (e.g., potassium bromide),
Contains other developer fog inhibitors.

The additives exemplified in each of the above processing steps and the amounts added thereof are well known in color photographic processing methods.

After color development, color photographic materials are usually bleached and fixed. Bleaching and fixing can also be combined into a bleach-fixing bath. Many compounds are used in bleaching agents, among them ferricyanates, dichromates, and water-soluble iron (II).
[) salt, water-soluble cobalt (Ill) salt, water-soluble copper (II) salt
) salts, water-soluble quinones, nitrosophenols, iron (IJ
I), complex salts of polyvalent cations and organic acids such as cobalt (■), and copper (II), and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, and N-hydroxyethylethylenediaminetriacetic acid. , metal complexes such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, copper complex salts of j,4-dipicolinate, and peracids such as argyl peracids, persulfates, permanganates, persulfates, etc. hydrogen oxide, hypochlorite,
Commonly used are chlorine, bromine, sardine powder, etc. alone or in appropriate combinations. This treatment solution is further used in U.S. Patent No. 3.
0hiroλ.

No. 3.20, No. 3.2, No. 266, Akihiro Shibu-r
S o number, Dohiro S-za 131. Various additives can also be added, including the bleaching accelerators described in No.

Any conventionally known fixing solution can be used for fixing. That is, ammonium, sodium, and potassium salts of thiosulfate are used as fixing agents at a concentration of 30 to 200 g/l, and in addition, stabilizers such as sulfites and isomeric bisulfites, and hardeners such as potassium alum are used. Membrane agents, pH buffers such as acetates, borates, etc. can be included. The fixer has a pH greater than or less than the pHJ.

U.S. patent for bleach bath, fixing bath, and bleach-fixing bath! ,
The methods described in J♂λ, No. 32, JP-A Akihiro f-10/RI-3, German Patent Nos. 1,06/, 117, etc. can also be applied.

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

Example 1 Polymer coupler of the present invention (1) θ, 7θy (/ , /
mmol equivalent) and the comparative coupler 0,7/,jq (/, equivalent to 1 mmoJ) represented by the following chemical structural formula fa) were dissolved in ethyl acetate of λθ hemp and 10 ml of ethanol, and a color developing agent was added to the solution. N: c chill N (2-methanesulfonamidoethyl)amino~λ-
suspending methylaniline l sulfate/JmmoA;
Next, add anhydrous sodium carbonate/2.7 mmol
An aqueous solution of water was added thereto and stirred at room temperature. 2. Potassium persulfate is added to this mixture. ≠10 containing mmol
ml of aqueous solution was gradually added dropwise.

After stirring well for 1 hour at room temperature, add 3 ml of ethyl acetate and
An extraction operation was performed by adding 0 ml of water. After thoroughly washing the ethyl acetate layer with saturated brine, the solvent was removed and the residue was separated using silica gel column chromatography. Elution e was first carried out with ethyl acetate/benzene ///, and then the polymer component was removed using ethyl acetate/methanol-=l/I.

113 ■ α Comparative coupler (at) The visible absorption spectral characteristics of magenta dyes formed from polymer coupler ■ and comparative coupler (al) in ethyl acetate are shown in Table/.

As shown in Table 1, the polymer coupler of the present invention is
- There is no sub-absorption near 30 nm, and the tail on the long wavelength side is sharply cut, which is advantageous in terms of color reproduction when used in color photographic materials.

Example 2 To 13 g of the polymer coupler (1) of the present invention and the polymer coupler (, If), 1', 7!1 of the present invention, jml of trioctyl phosphate and 110 g of ethyl acetate were added and dissolved, and this solution was diluted with gelatin. 10% aqueous gelatin solution containing sodium 5ee-butylnaphthalenesulfonate/
00g and stirred and emulsified using a homogenizer emulsifying machine to obtain an emulsion. This emulsion was converted into a green-sensitive silver chlorobromide emulsion (B
r:≠! m ol 'ir, α:j! mo1%)3
0'gC silver i3. rg), a coating aid (sodium dodecylbenzenesulfonate), and a hardening agent (2-hydroxy-≠.

t-dichloro-8-1 riazine) was added and coated onto a cellulose triacetate support. Furthermore, apply a gelatin coating solution as a protective layer on top of this layer. Gelatin/Fl/m2
) They were dried to form films A and B, respectively.

On the other hand, Film C was prepared in the same manner as Film A using comparative polymer coupler (a)/≠, j'g represented by the following structural formula.

H3 e Comparative coupler (a) Also, if the comparative coupler Cbl represented by the following structural formula is 1
Use 3g of ethyl acetate/! Finally, Film C was prepared in the same manner as Film A except that trml was used instead of trioctyl phosphate.

Comparative coupler (b) The above films A-D were exposed with a photosensitive needle at 7000 lux for 1 second and processed with the following processing solution.

Developer benzyl alcohol l! ; ml diethylenetriaminej acetic acid jg KBr θ,≠1 Na2SO3ji Na2CO330jq hydroxylamine sulfate 2g guamino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline 3/2H2SO4.H2O. ! y Make 100ml with water pE-110,/Bleach-fix ammonium thiosulfate (70wt%) 130ml Na2SO36g Na(Fe(EDTA)) '701 EDTA 1 Make iooomivc with water pH7,f Treatment process Temperature Time Developer 33° 3 minutes and 30 seconds bleach-fix solution 33° 7 minutes and 30 seconds water washing 2t~350 After processing for 3 minutes, the dye density was measured using a Magbeth densitometer Status AA filter. The spectral absorption spectrum of the dye image was also measured. The results are shown in Table 1. From Table 1, it can be seen that the absorption of the dye image in the film is similar to Example 1, with no sub-absorption and a tail on the long wavelength side.

Moreover, the polymer coupler of the present invention is conventional! - It is clear that it provides sufficient color density compared to pyrazolone type couplers.

Table λ

Claims (1)

[Claims] The following general formula (U, (IIJ, or (4)) capable of forming a dye by coupling with an oxidized product of an aromatic-grade amine developer
Silver halide color photographic light-sensitive material, characterized in that the silver halide emulsion layer contains a polymer or copolymer magenta color image-forming polymer coupler latex having repeating units derived from the monomer represented by: General formula (DR) ■ In the formula, R1 represents a hydrogen atom, a lower alkyl group having l-≠ carbon atoms, or a chlorine atom, R2, R3, and R4 represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a cup. Represents a ring leaving group. A represents -NHCO-, -0CO-1 or a phenylene group, B represents an unsubstituted or substituted alkylene group, an aralkylene group or a phenylene group, and the alkylene group may be linear or branched. Y is 10-1-NH-1-S-1-8O-1-SO2-
1-CONH-1-COO-1-Nl(CO-1-NH
Represents CONH-. m1n is m = / when n = 7
, when n=O, m=0 or /.