JPH0248099B2 - HAROGENKAGINKARAAKANKOZAIRYO - Google Patents

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 primary amine developer. When a silver halide color photographic material is subjected to color development after exposure, the oxidized aromatic primary amine developer reacts with the coupler to produce indophenol,
It is known that indoaniline, indamine, azomethine, phenoxazine, phenazine and similar dyes are produced to form color images.
In this method, a subtractive color method is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, which has a relationship with the remaining colors, respectively.
Magenta, and cyan color image forming agents are used. To form a yellow image, for example, an acylacetanilide or benzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone coupler is mainly used. , primarily phenolic couplers such as phenols and naphthols are used to form cyan images. Color couplers must meet various requirements, such as having good spectral properties;
There is a need for color development to provide dye images that exhibit a high degree of stability to light, temperature, and humidity over long periods of time. By the way, in multilayer color photosensitive materials, it is necessary to fix each coupler in separate layers in order to reduce color mixture and improve color reproduction. Many methods are known for making couplers diffusion resistant. 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 the need to thin the emulsion layer. This will have the opposite result. Another method of making a coupler resistant to diffusion is to substitute a polymerizable group on the coupler and use a polymer coupler latex obtained by polymerizing the group. Conventional methods for adding polymer couplers to hydrophilic colloid compositions in the form of latexes include adding latexes 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 an aqueous gelatin solution in the form of a latex. Examples of the former emulsion polymerization method are described in US Pat. No. 3,370,952 for emulsion polymerization in aqueous gelatin, and US Pat. No. 4,080,211 for emulsion polymerization in water. An example of a method for dispersing the latter in the form of a lipophilic polymer coupler latex is described in US Pat. No. 3,451,820. The method of adding polymeric 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.
Furthermore, since the latex can contain a high concentration of monomeric coupler, it is possible to easily incorporate a high concentration of coupler into the emulsion without increasing the viscosity. Furthermore, it has the advantage that there is no color mixing due to its completely non-migration property, and that there is little precipitation of the coupler in the emulsion film. Among such polymer couplers, magenta polymer couplers added to gelatin silver halide emulsions in latex form are disclosed, for example, in US Pat. No. 4,080,211, British Patent No. 1,247,688,
It is described in No. 3451820, No. 3926436, West German Patent No. 2725591, etc. However, in general, the absorption waveform of the magenta color image formed by the conventionally known magenta polymer coupler latex is broader than that of the color image formed by the same type of magenta coupler that has not been polymerized, and therefore the color reproducibility is had the problem of deterioration. In addition, in magenta polymer coupler latexes having a matrix of 5-pyrazolones, which have been mainly studied in the past, unnecessary absorption of yellow components exists in the vicinity of 430 nm, causing color turbidity. By the way, the use of 1H-[3,2-C]-S-triazoles (compounds that are not polymers) as magenta couplers is described in U.S. Pat. No. 3,725,067; In addition to having low properties, ordinary developers have relatively low coupling activity. Therefore, in order to add the required amount to the silver halide emulsion layer in the form of an oil dispersion, the thickness of the emulsion layer must be increased, which often leads to deterioration in sharpness. Accordingly, an object of the present invention is to provide a novel magenta color image-forming polymer coupler latex in which the absorption waveform of the magenta color image formed is sharp and has excellent color reproducibility. A second object of the present invention is to provide a novel magenta color image-forming polymer coupler latex which has extremely excellent color development properties. A third object of the present invention is to provide a novel magenta color image-forming polymer coupler latex which does not absorb unnecessary yellow components and gives a magenta color image without color turbidity. A fourth object of the present invention is to provide a color photographic material with high film strength. A fifth object of the present invention is to provide a color photographic material with a thin film and improved sharpness. The above-mentioned objects of the present invention are to provide a magenta color image-forming polymer coupler latex of a polymer or copolymer having a repeating unit derived from a monomer represented by the following general formula [] or [] having a pyrazolotriazole skeleton. This was achieved by incorporating it into a silver halide emulsion. [In the formula, R ₁ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and R ₂ and R ₃ represent a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an aryl group, Heterocyclic group composed of 5 to 6 atoms, alkylamino group, acylamino group, anilino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl group or sulfonamide group In the formula, X represents a coupling-off group linked via a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom or a sulfur atom. A is -NHCO
-, -OCO- or a phenylene group, and B represents an unsubstituted or substituted alkylene group, aralkylene group or phenylene group, and the alkylene group may be linear or branched. Y is -O-, -NH
−, −S−, −SO−, −SO ₂ −, −CONH−, −
Represents COO-, -NHCO- or -NHCONH-. m and n represent m=1 when n=1, and m=0 or 1 when n=0. ] R ₂ , R ₃ , X, and B in the general formulas [] and [] will be explained in more detail. R ₂ and R ₃ are hydrogen atoms,
In addition to the hydroxyl group, each unsubstituted or substituted alkyl group (preferably one having 1 to 20 carbon atoms; for example, a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group, a tridecyl group, etc.),
Aryl group (preferably one with 6 to 20 carbon atoms; for example, phenyl group, 4-t-butylphenyl group,
2,4-di-t-amyl phenyl group, 4-methoxyphenyl group, etc.), heterocyclic groups (e.g., 2-furyl group, 2-thienyl group, 2-pyrimidinyl group,
(2-benzothiazolyl group, etc.), alkylamino group (preferably one with 1 to 20 carbon atoms, such as methylamino group, diethylamino group, t-butylamino group, etc.), acylamino group (preferably one with 2 to 20 carbon atoms),
20 things. For example, acetylamino group, propylamide group, benzamide group, etc.), alinino group (for example, phenylamino group, 2-chloroanilino group, etc.), alkoxycarbonyl group (preferably one with 2 to 20 carbon atoms. For example, methoxycarbonyl group, butoxy carbonyl group, 2-ethylhexyloxycarbonyl group, etc.), alkylcarbonyl group (preferably one having 2 to 20 carbon atoms; for example, acetyl group, butylcarbonyl group, cyclohexylcarbonyl group, etc.), arylcarbonyl group (for example,
Preferably one having 7 to 20 carbon atoms. benzoyl group,
(4-t-butylbenzoyl group, etc.), alkylthio group (preferably one with 1 to 20 carbon atoms, such as methylthio group, octylthio group, 2-phenoxyethylthio group, etc.), arylthio group (preferably one with 6 to 20 carbon atoms) 20 (e.g. phenylthio group, 2-butoxy-5-t-octylphenylthio group, etc.),
Carbamoyl group (preferably one with 1 to 20 carbon atoms. For example, N-ethylcarbamoyl group, N,N
-dibutylcarbamoyl group, N-methyl-N-butylcarbamoyl group, etc.), sulfamoyl group (preferably one having up to 20 carbon atoms. For example, N-ethylsulfamoyl group, N,N-diethylsulfamoyl group, , N-dipropylsulfamoyl group, etc.) or a sulfolamide group (preferably one having 1 to 20 carbon atoms; for example, a methanesulfonamide group,
benzelsulfonamide group, p-toluenesulfonamide group, etc.). X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), a coupling-off group connected by an oxygen atom (e.g., an acetoxy group, a propanoyloxy group, a benzoyloxy group, an ethoxyoxaloyloxy group, a pyruvinyloxy group) , cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 2-naphthoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 2
- Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetra soloxy group, 2
-benzothiazolyloxy group, etc.), a coupling-off group connected via a nitrogen atom (e.g., Japanese Patent Application No. 1987-
What is described in No. 189538. Specifically, benzenesulfonamide group, N-ethyltoluenesulforamide group, heptafluorobutanamide group,
2,3,4,5,6-pentafluorobenzamide group, octanesulforamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl -2,4-dioxo-3-oxazolidinyl group, 1-benzyl-5-ethoxy-3-hydantoynyl group, 2-oxo-1,2-dihydro-1-
Pyridinyl group, imidazolyl group, pyrazolyl group,
3,5-diethyl-1,2,4-triazole-
1-yl group, 5- or 6-promo-benzotriazol-1-yl group, 5-methyl-1,2,
3,4-triazol-1-yl group, benzimidazolyl group, etc.), coupling-off groups linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methocacy-5-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2-cyanoethylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolyl group, etc.) represent B is unsubstituted or substituted with 1 to 10 carbon atoms,
It represents an alkylene group, an aralkylene group, or a phenylene group, and the alkylene group may be linear or branched. Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene,
Hexamethylene, decylmethylene, aralkylene groups such as benzylidene, phenylene groups such as p-phenylene, m-phenylene,
Examples include methylphenylene. In addition, substituents for the alkylene group, aralkylene group, or phenylene group represented by B include an aryl group (for example, a phenyl group, etc.), a nitro group, a 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. methane group etc.) sulfonamide group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, etc.), halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), carboxy group, carbamoyl group (e.g., methylcarbamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), sulfonyl group (eg, methylsulfonyl group, etc.), and the like. When there are two or more of these substituents, they may be the same or different. In the general formulas [] and [] of the present invention,
R ₁ is particularly preferably a hydrogen atom or a lower alkyl group (particularly a methyl group), R ₂ and R ₃ are particularly preferably a hydrogen atom, an alkyl group, or an aryl group, and X is a hydrogen atom, a halogen atom, or a nitrogen atom. A coupling-off group is particularly preferred, and when n=1, Y is -NHCO
- is particularly preferred, B when m = 1 is particularly preferably an unsubstituted alkylene group, aralkylene group or phenylene group, and A is -NHCO
- is particularly preferred. Next, preferred specific examples of the monomeric couplers of the general formulas [] and [] of the present invention will be given. The monomeric couplers of the above general formulas [] and [] are generally obtained by the method described in U.S. Pat. It can be synthesized by reaction with chloride. Next, synthesis examples of monomeric couplers of the general formula [] or [] will be shown. Production method example 1 3-[3-(3-acrylamidofer)-propyl-6-methyl-1H-prazolo-[3,2-
Synthesis of C]-S-triazole (C-5)
[3-(3-aminophenyl)-propyl]-6-methyl-1H-pyrazolo[3,2-C]-S-triazole 25.5 g (0.1 mol) was mixed with 200 ml of acetonitrile,
It was dissolved in 100 ml of dimethylacetamide, 16 ml of pyridine, and 1 ml of nitrobenzene. 9.5 g (0.105 mol) of acrylic acid chloride was slowly added dropwise, and after a stirring reaction of 1 hour at 10° C. or lower, water and ethyl acetate were added to perform an extraction operation. After thoroughly washing the ethyl acetate layer with saturated brine, the solvent was removed and crystallization was performed with acetonitrile. Recrystallization was performed with acetonitrile to obtain 20.6 g of C-5. Melting point 195℃～197℃ Elemental analysis (C ₁₇ H ₁₉ N ₅ O) (Theoretical value) C: 65.99% H: 6.20% N: 22.64% (Experimental value) C: 65.78% H: 6.23% N: 22.52% etc. The monomeric coupler can also be synthesized according to the above method. The polymer coupler latex of the present invention may be a homopolymer of monomeric couplers of general formula [] or [], or a copolymer of monomeric couplers of general formula [] and []. , a monomeric coupler of the general formula [] and/or [] and a non-color-forming ethylene-like monomer that does not couple with the oxidation product of an aromatic primary amine developing agent. In any of the above cases, two or more types of monomeric couplers included in the general formula [] may be used as the monomeric coupler of the general formula [], and similarly, monomeric couplers of the general formula [] Two or more types of monomeric couplers included in the general formula [] may be used. Among the above, a copolymer of a monomeric coupler of the general formula [] or [] and the non-color-forming ethylene-like monomer is preferred. Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-
Alacrylic acid (e.g. methacrylic acid), esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide,
Methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n
-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate, and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine , and 2- and 4-
Examples include 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 ethylenically unsaturated monomers to be copolymerized with the monomeric couplers corresponding to the general formulas [] and [] depend on the physical properties of the copolymer formed and/or Chemical properties such as solubility, compatibility with binders such as gelatin of the photographic colloid composition, its flexibility, thermal stability, etc. can be selected to be influenced. Also from this point of view, acrylic esters, methacrylic esters, and maleic esters are preferred copolymerization components. 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 the form of a latex in an aqueous gelatin solution as described above. Alternatively, it may be produced by a direct emulsion polymerization method. The method described in US Pat. No. 3,451,820 can be used for emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, and the method described in US Pat. Nos. 4,080,211 and 3,370,952 can be used for emulsion polymerization. The synthesis of the magenta polymer couplers of the present invention consists of
As a polymerization initiator and polymerization solvent, JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-
This can be carried out using compounds described in JP-A-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044, and JP-A-57-29638. The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc.
Possible from below to 100℃, but usually 30℃ to 100℃
It is preferable to polymerize within the range of . General formula occupied in polymer coupler [],
The proportion of the colored portion corresponding to [] is normally desirably 5 to 80% by weight, but is preferably 20 to 70% by weight in terms of color reproducibility, color development and stability. In this case, the equivalent molecular weight (grams of polymer containing 1 mole of monomeric coupler) is preferably about 250 to 400, but is not limited thereto. An example of a method for producing a polymer coupler is shown below. (Production method) Production method example 2 6-methyl-3-[3-(3-acrylamide)
-propyl]-1H-pyrazolo-[3,2-C]-
Copolymer coupler of S-triazole (C-5) and butyl acrylate (lipophilic polymer coupler ()) A mixture of 20 g of monomer coupler (C-5), 20 g of butyl acrylate, and 200 ml of dioxane was stirred in a nitrogen stream for 80 minutes. After heating to ℃, 20 ml of dioxane containing 0.5 g of dimethyl azobisisobutyrate was added to initiate polymerization. After reacting for 5 hours, the reaction solution was cooled,
The precipitated solid was poured into 1.5 ml of water and was washed thoroughly with water. By heating and drying this solid under reduced pressure, 38.9 g of lipophilic polymer () was obtained. This polymer coupler is a monomer coupler (C-5) with 50.2% copolymer formed by nitrogen analysis.
It was shown that it contains Next, a method for dispersing the lipophilic polymer coupler (2) in an aqueous gelatin solution in the form of a latex will be described. First, two solutions (a) and (b) were prepared as follows. (a) Heat 200 g of a 3.0% by weight aqueous solution of bone gelatin (PH5.6 at 35°C) to 38°C and add 16 ml of a 10% by weight aqueous solution of sodium lauryl sulfate. (b) 20g of the above lipophilic polymer coupler ()
Dissolve in 200 ml of ethyl acetate at °C. Next, solution (b) was put into an explosion-proof mixer that was being stirred at high speed, and solution (a) was rapidly added thereto and stirred for 1 minute, then the mixer was stopped and ethyl acetate was removed by distillation under reduced pressure. . A latex (') was thus prepared by dispersing the lipophilic polymer coupler in a dilute gelatin solution. Production method example 3 3-methacrylamido-6-methyl-1H-pyrarozo[3,2-C]-S-triazole (C
-2) and a copolymer coupler of ethyl acrylate and methacrylic acid (lipophilic polymer coupler ()) A mixture of 20 g of monomer coupler (C-2), 10 g of ethyl acrylate, 5 g of methacrylic acid, and 200 ml of n-propanol was heated under nitrogen. After heating to 80° C. under stirring in a gas stream, 20 ml of n-propanol containing 0.3 g of dimethyl azobisisobutyrate was added to initiate polymerization. 5
After reacting for a period of time, the reaction solution was cooled, poured into water 1 to separate the precipitated solid, and washed thoroughly with water.
By heating and drying this solid under reduced pressure, 32.5 g of lipophilic polymer (2) was obtained. This polymer coupler is a monomer coupler (C-2) with 59.1% copolymer formed by nitrogen analysis.
It was shown that it contains Next, a method for dispersing the lipophilic polymer coupler (2) in an aqueous gelatin solution in the form of a latex will be described. First, two solutions (a) and (b) were prepared as follows. (a) 30% by weight aqueous solution of bone gelatin (at 35°C)
Heat 200g of PH5.6) to 38℃ and add 16ml of a 10% by weight aqueous solution of sodium lauryl sulfate. (b) 20g of the above lipophilic polymer coupler ()
Dissolve in 200 ml of ethyl acetate at °C. Next, solution (b) was put into an explosion-proof mixer that was being stirred at high speed, and solution (a) was rapidly added thereto and stirred for 1 minute, then the mixer was stopped and ethyl acetate was removed by distillation under reduced pressure. . A latex (') was thus prepared by dispersing the lipophilic polymer coupler in a dilute gelatin solution. Manufacturing method example 4 7-{1,2-benziisothiazole-3 (2H)
-one-2-yl}-3-methacrylamide-
6-Methyl-1H-pyrazolo[3,2-C]-S
- Copolymer coupler of triazole (C-18) and butyl acrylate (lipophilic polymer coupler ()) A mixture of 20 g of monomer coupler (C-18), 20 g of butyl acrylate, and 200 ml of dioxane is heated to 80°C in a nitrogen stream. After that, 20 ml of dioxane in which 0.4 mg of azobisisobutyronitrile was dissolved was added to initiate polymerization. After reacting for 3 hours, the temperature was raised to 100°C and the reaction was further continued for 2 hours. Next, after cooling the reaction solution, add 2
The precipitated solid was separated and washed thoroughly with water. By heating and drying this solid under reduced pressure, 37.9 g of lipophilic polymer coupler (2) was obtained. This polymer coupler is a monomer coupler (C-18) with 50.5% copolymer formed by nitrogen analysis.
It was shown that it contains Next, a method for dispersing a lipophilic polymer coupler (2) in an aqueous gelatin solution in the form of a latex will be described. First, two solutions (a) and (b) were prepared as follows. (a) 30% by weight aqueous solution of bone gelatin (at 35°C)
PH5.6) Heat 200g to 38℃ and add 16ml of a 10% by weight aqueous solution of sodium lauryl sulfate. (b) 38g of the above lipophilic polymer coupler ()
Dissolve in 200 ml of ethyl acetate at °C. Next, solution (b) was put into an explosion-proof mixer that was being stirred at high speed, and solution (a) was rapidly added thereto and stirred for 1 minute, then the mixture was stopped and ethyl acetate was removed by distillation under reduced pressure. . A latex (') was thus prepared by dispersing the lipophilic polymer coupler in a dilute gelatin solution. Production Examples 5 to 20 Next, the following lipophilic polymer couplera was produced in the same manner as the copolymers of Production Examples 2 to 4 (Production Process).

[Table] (Production method) Production method example 21 3-Methacrylamide-6-methyl-1H-pyrazolo-[3,2-C]-S-triazole (C
-2) and a copolymer polymer coupler of butyl acrylate and methyl acrylate (polymer latex coupler (A)) oleyl methyl tauride 1 in the flask of 3
An aqueous solution of 1.2 g containing 1.2 g was heated to 80° C. while stirring and passing a nitrogen stream, and after adding 15 ml of a 2% aqueous solution of potassium persulfate to the aqueous solution, 20 g of monomer coupler (C-2), 10 g of butyl acrylate, A solution prepared by heating and dissolving 10 g of methyl acrylate in 500 ml of methanol was added dropwise over 20 minutes. After reacting for 1 hour, 5% aqueous solution of potassium persulfate was added.
Added ml. After reacting for an additional hour, methanol and water were distilled off. After cooling the formed latex, the latex solution was adjusted to pH 6.0 with 1N sodium hydroxide. The polymer concentration of the latex formed was 5.0%, and nitrogen analysis showed that the monomeric coupler (C-
2) was included. Manufacturing method example 22 6-methyl-3-[3-(3-acrylamide)
-propyl]-1H-pyrazolo-[3,2-C]-
Copolymer latex of S-triazole (C-5) and butyl acrylate (polymer latex coupler (B)) Oleyl methyl tauride in flask 1
400 ml of an aqueous solution containing 2.2 g was heated to 80°C while stirring and passing a nitrogen stream, and 2 ml of a 2% aqueous solution of potassium persulfate and 4 ml of butyl acrylate were added to the aqueous solution.
g added. After 1 hour monomeric coupler (C-5) 20
g, butyl acrylate 10g, ethanol 200ml
was added, and then 20 ml of a 2% aqueous solution of potassium persulfate was added. After reacting for 2 hours, ethanol and unreacted butyl acrylate were distilled off. After cooling the formed latex, the latex solution was adjusted to pH 6.0 with 1N sodium hydroxide. The latex formed contained 9.6% polymer and nitrogen analysis showed 57.1% monomeric coupler (C-5) in the polymer.
It was shown that it was included. Production Examples 23 to 34 Next, the following polymer coupler latexes were produced in the same manner as Production Examples 21 and 22 (Production Process).

[Table] The magenta polymer coupler latex of the present invention can be used alone or in combination of two or more. The magenta polymer coupler latex of the present invention can also be used in combination with magenta polymer coupler latexes described in US Pat. No. 4,080,211, British Patent No. 1,247,688, and the like. In addition, the magenta polymer coupler of the present invention
Hydrophobic magenta coloring couplers are added to the latex, such as U.S. Pat.
No. 3062653, No. 3127269, No. 3311476, No.
No. 3419391, No. 3519429, No. 3558319, No.
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417975, OLS No. 2418959,
No. 2424467, Special Publication No. 6031, No. 40-6031, No. 51-
No. 20826, No. 52-58922, No. 49-129538, No. 49
−74027, No. 50-159336, No. 52-42121, No.
No. 49-74028, No. 50-60233, No. 51-26541,
Magenta described in No. 53-55122, etc. The coupler is used in US Pat.
No. 2304940, No. 2311020, No. 2322027, No.
No. 2360289, No. 2772163, No. 2801170, No.
No. 1801171, No. 3619195, British Patent No. 1151590,
A dispersion dispersed in a hydrophilic colloid by the method described in German Patent No. 1143707 etc. can be impregnated (loaded) by the method described in JP-A-51-39853 etc. The magenta coupler is impregnated (loaded) into the magenta polymer coupler latex of the present invention by the method described in JP-A-51-59942, JP-A-54-32552, US Pat. No. 4,199,363, etc.
It can also be used. Impregnated (loaded) here means a state in which the hydrophobic magenta coupler is contained within the magenta polymer coupler latex or is deposited on the surface of the magenta coupler latex. However, the exact mechanism by which impregnation (loading) occurs is not known. The magenta polymer coupler latex of the present invention has been developed in U.S. Pat.
No. 3733201, No. 3617291, No. 3703375, No. 3733201, No. 3617291, No. 3703375, No.
No. 3615506, No. 3265506, No. 3620745, No. 3620745, No.
No. 3632345, No. 3869291, No. 3642485, No.
No. 3770436, No. 3808945, British Patent No. 1201110,
U.S. Pat. No. 1,236,767, etc., the development inhibitor releasing (DIR) couplers described in U.S. Pat.
No. 2272191, No. 2304940, No. 2311020, No. 2311020, No. 2304940, No. 2311020, No.
No. 2322027, No. 2360289, No. 2772163, No. 2322027, No. 2360289, No. 2772163, No.
2801170, 2801171, 3619195, British Patent No. 1151590, German Patent No. 1143707, etc., a dispersion dispersed in a hydrophilic colloid was prepared in JP-A-51
It can also be used by impregnating the magenta polymer coupler latex with the DIR coupler as described above.
51-59942, 54-32552, and U.S. Pat. No. 4,199,363. Also, German Publication No. 2529350, German Publication No. 2448063, German Publication No.
No. 2610546, U.S. Patent No. 3928041, U.S. Patent No. 3958993,
Same No. 3961959, No. 4049455, No. 4052213, Same No.
No. 3379529, No. 3043690, No. 3364022, No. 3379529, No. 3043690, No. 3364022, No.
DIR compounds described in No. 3297445, No. 3287129, etc. can also be used in combination. The magenta polymer coupler latex of the present invention is also disclosed in US Patent No. 2449966 and West German Patent No.
No. 2024186, JP-A-49-1233625, JP-A No. 49-131448
Colored magenta coupler described in U.S. Pat. No. 52-42121, U.S. Pat.
No. 2998314, No. 2808329, No. 2742832,
Competitive couplers described in U.S. Patent No. 2689793, U.S. Patent No. 2336327, U.S. Pat.
Stain inhibitors described in No. 2403721, No. 2701197, No. 3700453, British Patent No. 1326889, US Patent No. 3434300, No. 3698909, No. 3574627,
It can also be used in combination with dye image stabilizers described in Nos. 3573050 and 3764337. Generally well-known couplers other than magenta-forming couplers can be used to make color photographic materials using the present invention. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions.
It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development. The coupler may be one 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, benzoylacetalinide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include the U.S. patent
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 3891445, West German patent No. 1547868, West German application
No. 2219917, No. 2261361, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783, No. 1978, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
It is described in No. 51-21827, No. 50-87650, etc. As the cyan color-forming coupler, a phenol compound, a naphthol compound, etc. can be used. Specific examples are US Patent Nos. 2369929 and 2434272.
No. 2474293, No. 2521908, No. 2895826,
Same No. 3034892, No. 3311476, No. 3458315, Same No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, No. 4004929, West German patent application 2414830
No. 2454329, JP-A-48-59838, No. 51-
No. 26034, No. 48-5055, No. 51-146828, No. 55
-Described in No. 73050. 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 the method described in US Pat. . 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 halide emulsion used in the present invention consists of mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. in addition to silver chloride and silver bromide, and contains hydrophilic materials such as gelatin. It is finely dispersed in a synthetic polymer, and can be dispersed in a wide range of states, from those with uniform particle size to those with a wide particle size distribution, and with an average particle size of about 0.1 micron to about 3 microns. One is selected depending on the intended use of the photosensitive material. Furthermore, these silver halide emulsions may be chemically sensitized such as sulfur sensitization, gold sensitization, or reduction sensitization, or may contain sensitivity-enhancing agents such as polyoxyethylene compounds and onium compounds. good. Furthermore, not only emulsions of the type that form latent images mainly on the surface, but also emulsions of the internal latent image type that form inside the grains can be used in the present invention. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Hydrophilic polymeric substances constituting the photosensitive layer of the present invention include proteins such as gelatin, polymeric nonelectrolytes such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide, acidic polymeric substances such as alginates and polyacrylates, Suitable are polyampholytes such as polyacrylamide treated by the Hofmann rearrangement reaction, copolymers of acrylic acid and N-vinylimidazole, crosslinkable polymers as described in US Pat. No. 4,215,195, and the like. 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 4-hydroxy-6-methyl-
A large number of compounds including 1,3,3a,7-tetrazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, etc. It has been known since ancient times. An example of a compound that can be used is “Research
Disclosure”17643 (November 1978 issue) page 24
The original literature is listed in the Antifoggand and Stabilizer section. 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 Sanipon, nonionic surfactants such as alkylene oxide, glycerin, and glycidol,
Higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphonium or sulfonium, carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester groups,
They are classified into anionic surfactants containing acidic groups such as phosphate groups, and amphoteric surfactants such as amino acids, aminosulfones, and sulfuric or phosphoric acid esters of amino alcohols. Spectral sensitivity and supersensitization of photographic emulsions can be achieved by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes and the like. These color sensitization techniques have been known for a long time.
U.S. Patent No. 2688545, U.S. Patent No. 2912329, U.S. Patent No. 3397060,
No. 3615635, No. 3628964, British Patent No. 1195302,
No. 1242588, No. 1293862, West German patent publication
No. 2030326, No. 2121780, Special Publication No. 43-4936, No.
There is also a description in No. 44-14303, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, the sensitivity, etc., and the purpose and use of the photosensitive material. 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 aldebide compounds such as 2-phenoxy-3-chlormaalaldehydic acid described in Japanese Patent Publication No. 1872/1972 are also useful in the present invention in many cases. Yes, but
Compounds having multiple epoxy rings described in Japanese Patent Publication No. 34-7133, poly-(1-aziridinyl) compounds described in Japanese Patent Publication No. 37-8790, and US Pat. Nos. 3362827 and 3325287. active halogen compounds, U.S. Patent No. 2994311,
Non-aldehyde crosslinking agents such as vinyl sulfone compounds known from Belgian Patent No. 3582322 and Belgian Patent No. 686440 are 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 polymer. In particular, papers coated with polyethylene, polypropylene, ethylene-butene copolymers, etc., and plastic films with a roughened surface as shown in Japanese Patent Publication No. 47-19068 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 light-blocking by adding carbon black, etc. You can choose from the following. Each layer of the photographic material can be applied by a variety of coating methods including dip coating, air knife coating, curtain coating, or extrusion coating using a hopper as described in US Pat. No. 2,681,294. U.S. patents if required
No. 2761791, No. 3508947 and No. 2941898, No.
It is also possible to apply two or more layers at the same time by methods such as those described in No. 3,526,528. 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. It can also be realized in a so-called mixed packet type, in which emulsions of different properties are mixed and coated on a support. The photosensitive material of the present invention can be realized in various forms. For example, color negative film, color positive film, color reversal film,
There are color photographic papers, color reversal photographic papers, etc. In order to obtain a dye image of the color photographic material of the present invention, development processing is required after exposure. The development process basically includes color development; bleaching; and fixing steps. In this case, each process may be independent, or two or more of the processes may be performed in a single process using processing liquids that have those functions. 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),
Various steps such as stabilization and water washing are combined as necessary. The processing temperature is set within a preferred range depending on the photosensitive material and processing recipe, but is generally 18°C.
It is often set between 6°C and 6°C. Note that it is not necessary that the set temperature for each step in the series of processing be the same. The color developer contains a compound whose oxidation product reacts with a color former called a coupler to form a color product, that is, a developing agent, and has a pH of 8 or more, preferably 9 to 9.
12 alkaline aqueous solution. The main developing solution is 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, 4-amino-N,N diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline 4
-amino-3-methyl-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-
N,N-dimethylaniline, 4-amino-3-methoxy-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline, 4-amino-3-methoxy- N-
Ethyl-N-β-methoxyethylaniline, 4-
Amino-3-β-methanesulfamide ethyl-
N,N-dimethylaniline and its salts (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) are listed as preferred representative examples. Other U.S. Patents No. 2193015, U.S. Patent No. 2592364,
JP-A-48-64933 or written by LFAMason
Photographic Processing Chemistry (Focal
Press-London edition, 1966), pages 226-229T.
“The Theory of the Photographic” by H.James
Process” (Macmillan, New York 4th edition (1977), pp. 315-325, etc.).
Also “The Theory of the Photographic
Aminophenols described in pp. 311-315 of "Process" (4th edition) may also be used.
- Combination use with pyrazolidones is also possible. Various additives can be added to the color developing solution as necessary. 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 strong bases such as acetic acid and boric acid, and their salts); Development accelerators (e.g. U.S. patent
Various pyridium compounds and cationic compounds described in Nos. 2648604 and 3671247, potassium nitrate and sodium nitrate, U.S. Patent No. 2533990,
Nonionic compounds such as polyethylene glycol condensates and their derivatives as described in British Patent No. 2577127 and British Patent No. 2950970, and polythioethers as represented by the compounds described in British Patent No. 1020033 and British Patent No. 1020032. compounds, polymer compounds with sulfite esters as typified by the compound described in US Pat. , alkali iodide and US patent
Including nitrobenzimidazoles described in No. 2496940 and No. 2656271, mercaptobenzimidazole, 5-methylbenztriazole, 1-phenyl-5-mercaptotetrazole, US patent
No. 3113864, No. 3342596, No. 3295976, No.
Compounds for rapid processing described in Nos. 3615522 and 3597199, thiosulfonyl compounds described in British Patent No. 972211, phenazine N oxides as described in Japanese Patent Publication No. 46-41675, and other scientific photographic handbooks. , Volume 2, pages 29 to 47), and other U.S. patents.
No. 31161513, No. 3161514, British Patent No. 1030442,
No. 1144481, No. 1251558, stain or sludge inhibitors, multilayer effect accelerators and preservatives (e.g. sulfites, acid sulfites, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite additives, etc.). 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, 1-phenyl-3-pyrazolidone, and N-methyl-p-aminophenol is used. In addition, inorganic salts such as sodium sulfate, PH regulators and buffers such as borax, boric acid, sodium hydroxide, and sodium carbonate, alkali halides (e.g., potassium bromide), and other developer fog preventive agents. It is included. 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 as whitening agents, among them ferricyanates, dichromates, water-soluble iron () salts, water-soluble cobalt () salts, water-soluble copper () salts, water-soluble quinones,
Nitrosophenols, iron (), cobalt (),
Complex salts of polyvalent cations such as copper () and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, malonic acid, tartaric acid, malic acid, diglycol acids, metal complex salts such as dithioglycolic acid, and 2,6
- Peracids such as dipicolinic acid copper complexes, such as alkyl peracids, persulfates, permanganates, hydrogen peroxide, hypochlorites, chlorine, bromine, sardine powder, etc. alone or in appropriate combinations. Common. This treatment solution further includes U.S. Patent No. 3042520,
Various additives may be added, including the bleach accelerators described in Japanese Patent Publication No. 3241966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 45-8836, and the like. Any conventionally known fixing solution can be used for fixing. That is, ammonium, sodium, and potassium salts of thiosulfate are used as fixing agents.
It is used in an amount of ~200g/, and may also contain stabilizers such as sulfites and isomeric bisulfites, hardening agents such as potash amepan, and PH buffers such as acetates and borates. . The fixer has a pH greater than or equal to 3. Regarding the bleaching bath, fixing bath, and bleach-fixing bath, the methods described in US Pat. The present invention will be explained in more detail with reference to Examples below. Example 1 0.68 g (equivalent to 1.1 mmol) of the coupler of the present invention and a comparative coupler represented by the following chemical structural formula (a)
0.76g (equivalent to 1.1mmol) of 20ml of ethyl acetate, 10
ml of ethanol, 1.3 mmol of 4-N-ethyl-N-(2-methanesulfonamidoethyl)amino-2-methylaniline monosulfate, a color developing agent, was suspended therein, and then anhydrous An aqueous solution of 12.9 mmol of sodium carbonate dissolved in 5 ml of water was added and stirred at room temperature. 10 ml of an aqueous solution containing 2.4 mmol of potassium persulfate was gradually dropped into this mixture. After stirring well at room temperature for 1 hour, 50 ml of ethyl acetate and 30 ml of water were added to perform an extraction operation. After thoroughly washing the ethyl acetate layer with saturated brine, the solvent was removed and the residue was separated using silica gel column chromatography. The eluent is ethyl acetate/benzene = 1/1.
The polymer component was then taken out using ethyl acetate/methanol=1/1. The visible absorption spectra in ethyl acetate of the magenta dye formed from the polymeric coupler and comparative coupler (a) are shown in FIG. The maximum concentration of both absorption spectra was normalized to 1.0 and compared. In FIG. 1, the solid line represents the visible absorption spectrum of the polymer coupler of the present invention, and the broken line represents the visible absorption spectrum of the comparative polymer coupler (a). As can be seen from Figure 1, the polymer coupler of the present invention has no sub-absorption in the vicinity of 400 to 430 nm and has a sharply cut tail on the long wavelength side, which is advantageous for color reproduction when used in color photographic materials. I understand. Example 2 13 g of the polymer coupler of the present invention and 8.7 g of the polymer coupler of the present invention were dissolved by adding 5 ml of trioctyl phosphate and 40 ml of ethyl acetate, respectively, and the solution was dissolved in a 10% solution containing sodium 1-see-butylnaphthalenesulfonate. gelatin aqueous solution
The mixture was added to 100 g and stirred and emulsified using a homogenizer emulsifying machine to obtain an emulsion. 300 g of this emulsion was used as a green silver chlorobromide emulsion (Br: 45 mol%, Cl: 55 mol%).
(contains 13.5 g of silver), coating aid (sodium dodecylbenzenesulfonate), hardener (2-
Hydroxy-4,6-dichloro-S-triazine) was added and coated onto a cellulose triacetate support. Furthermore, a gelatin coating solution was applied as a protective layer on this layer (1 g/m ² of gelatin) and dried to form films A and B, respectively. On the other hand, Film C was prepared in the same manner as Film A using 14.5 g of comparative polymer coupler (a) represented by the following structural formula. Also, a comparative coupler (b) represented by the structural formula below
Film C was prepared in the same manner as Film A except that 13 g of ethyl acetate was used, and 15 ml of ethyl acetate and 15 ml of trioctyl phosphate were used. The above films A to D were measured at 1000 lux 1 with a sensitometer.
It was exposed for 2 seconds and processed with the following processing solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxylamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-β-
(methanesulfonamide)ethylaniline 3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6. 8 Processing process Temperature Time Developing solution 33° 3 minutes 30 seconds Bleach-fixing solution 33° 1 minute 30 seconds Washing 28-35° 3 minutes Measure the dye image density after processing using a Macbeth densitometer Status AA filter. It was measured. 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. It is also clear that the polymer coupler of the present invention provides sufficient color density compared to conventional 5-pyrazolone type couplers.

【table】 [Brief explanation of drawings]

FIG. 1 shows the visible absorption spectrum when the polymer coupler of the present invention of Example 1 (solid line) and the comparative polymer coupler (a) (dashed line) were colored.

Claims (1)

[Scope of Claims] 1 The following general formula () capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developer,
A silver halide color photographic photosensitive material comprising a polymer or copolymer magenta color image-forming polymer coupler latex having repeating units derived from the monomer represented by () in the silver halide emulsion layer. material. In the formula, R ₁ represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and R ₂ and R ₃ represent a hydrogen atom, a hydroxyl group, an unsubstituted or substituted alkyl group, an aryl group, 5 A heterocyclic group composed of ~6 atoms, an alkylamino group, an acylamino group, anilino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, or a sulfonamide group In the formula, X represents a hydrogen atom, a halogen atom, or a coupling-off group linked via an oxygen atom, nitrogen atom, or sulfur atom. A is-
NHCO-, -OCO- or a phenylene group, B is an unsubstituted or substituted alkylene group,
It represents an aralkylene group or a phenylene group, and the alkylene group may be linear or branched. Y is -O
−, −NH−, −S−, −SO−, −SO ₂ −, −CONH
−, −COO−, −NHCO− or −NHCONH−
represents. m, n are m=1, n=0 when n=1
When m=0 or 1.