JPH01167840A - Novel photographic cyan coupler - Google Patents

Abstract

PURPOSE:To make clear a cyan image by improving the spectral absorption characteristic of a coupler, and to improve the durability of the title coupler against heat and humidity by incorporating a specified cyan polymer coupler in the photographic cyan coupler. CONSTITUTION:The cyan image is formed by incorporating a pyrazoloazole type cyan polymer coupler having a group capable of forming one or more of hydrogen bonds at a position capable of being substituted except the active point of the group, in the photographic cyan coupler. The coupler may contain a repeating unit derivated from a monomer shown by formula I, etc. In formula I, R1 is a group capable of forming a hydrogen bond, R2 and Y are each H or a substituting group, (l) is 0 or 1, X is H or a group capable of being released by allowing to react with the oxidant of a color developing main agent, Q1 is an ethylenic unsatd. group, etc. And the monomer shown by the formula is composed of a compd. shown by formula II, etc., and the polymer coupler is formed by copolymerizing the monomer and a (meth)acrylate, etc.

Description

[Detailed description of the invention]

[Field of Industrial Application] The present invention relates to a novel pyrazoloazole type cyan polymer coupler that forms a dye image with excellent dispersion stability, excellent spectral absorption characteristics, and excellent heat resistance and moisture resistance. [Background of the Invention] After a silver halide photographic material is exposed to light and subjected to color development processing, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. A color image is formed. Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images. Phenols or naphthols have been widely used as cyan image forming couplers. However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The reason is that the absorption is not sharp on the short wavelength side, and the edge region also has unnecessary absorption, that is, asymmetric absorption. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated. Furthermore, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability. For example, U.S. Patent Nos. 2 and 3
The dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 67.531 and U.S. Pat. Dye images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 772,162 generally have poor light fastness, and dye images obtained from the 1-hydroxy-2-naphthamide cyan coupler generally have poor light fastness. Poor light and heat fastness. Also, U.S. Patent No. 4,122,369 and Japanese Patent Application Publication No. 5
7-155538, JP-A-57-157246 and other specifications, and U.S. Patent No. 3,880,661.
The 2,5-diacylaminophenol cyan coupler having a hydroxyl group in the ballast portion described in the specification is still sufficiently satisfactory in terms of fastness to light and heat to preserve the dye image for a long period of time. level has not been obtained. Incidentally, in multilayer color photographic materials, in order to eliminate color mixing of each dye and improve color reproducibility, it is necessary to fix each coupler in each separate layer. Various methods have been known for imparting diffusion resistance to couplers for this purpose. One method is to introduce a long-chain aliphatic group into the coupler molecule, and the coupler is either alkali-soluble and added to an aqueous gelatin solution, or dissolved in a high-boiling organic solvent and emulsified and dispersed in an aqueous gelatin solution. . However, these couplers have the disadvantage of significantly increasing the viscosity of aqueous gelatin solutions or causing crystal precipitation in emulsions. Furthermore, high boiling point organic solvents require a large amount of gelatin to soften the emulsion layer, making it difficult to make the emulsion layer thin. On the other hand, there is a method of using a latex of a polymer coupler obtained by polymerizing a monomer coupler in which the coupler is made diffusion resistant and a group containing a polymerizable unsaturated bond is introduced into the coupler molecule. The polymer coupler can be added to the hydrophilic colloid composition in the form of a latex in one of two ways. One is to directly polymerize the coupler monomer together with other copolymerizable components by emulsion polymerization to form a latex, which is then added to a silver halide emulsion. Another method is to add the coupler monomer, if necessary, to
In this method, the polymer coupler is polymerized by solution polymerization together with other copolymerizable components, and the resulting polymer coupler is dissolved in a solvent, and then dispersed in an aqueous gelatin solution to form a latex. Regarding the former emulsion polymerization method, for example, US Pat.
370,952 and 4,080,211, etc., respectively. The latter solution polymerization method is described, for example, in US Pat. No. 3,451,820. The method of adding such polymer couplers in latex form to hydrophilic colloid compositions has the following advantages over other methods. That is, (1) the polymer coupler latex can contain a high concentration of coupler units. (2) The layer can be made thinner because it does not need to contain a high boiling point organic solvent for dispersing the coupler in the emulsion. (3) Since the film can be made thinner, image sharpness can be improved. (4) In addition, since the aqueous gelatin solution does not thicken much, high-speed uniform coating is possible and mass production is excellent. (5) Furthermore, since the polymer coupler is made into latex,
The strength of the formed film does not deteriorate. There are several examples of polymer couplers added to silver halide emulsions in the form of latexes, among which US Pat. No. 3,767,412 describes a cyan polymer coupler latex. has been done. However, this cyan polymer coupler also
Although it has many excellent advantages as a polymer coupler as mentioned above, since it is a phenolic polymer coupler, there are problems that need to be improved as mentioned above, such as color reproduction problems and dye image problems. There is a problem with thermal fastness, and a solution to this problem is desired. The present inventors have discovered that by using a pyrazoloazole compound with excellent color reproducibility and fastness to heat and humidity in the form of a polymer coupler, favorable results can be obtained in that it also has dispersion stability. , we have completed the present invention. [Object of the Invention] The first object of the present invention is to provide a novel pyrazoloazole-based polymer cyan coupler having a group capable of hydrogen bonding. The second object of the present invention is to create a new cyan coupler that improves the drawbacks of conventionally used cyan dye-forming couplers, that is, it has sharp absorption and less absorption in the blue and edge regions, which has so-called spectral absorption characteristics. An object of the present invention is to provide a polymer cyan coupler which forms an excellent and clear cyan image. A third object of the present invention is to provide a novel polymeric cyan coupler that forms a cyan image without causing any change in hue due to heat or humidity. A fourth object of the present invention is to provide a novel polymeric cyan coupler capable of forming a thin silver halide color photographic light-sensitive material with strong film strength. A fifth object of the present invention is to provide a photographic cyan polymer coupler having excellent dispersion stability. [Structure of the Invention] The above objects of the present invention have been achieved by a pyrazoloazole type cyan polymer coupler having at least one hydrogen bondable group at a substitutable position other than the active site. The present invention will be explained in detail below. The pyrazoloazole type cyan polymer coupler according to the present invention includes, for example, pyrazolo pyrazole compounds, pyrazoloimidazole compounds, pyrazolotriazole compounds, pyrazolotetrazole compounds, and pyrazolobenzimidazole compounds, Preferably below-
Formation [Ia] ~ [If'] and/or (Ila
] ~[IIg] It has a repeating unit derived from a monomer represented by [IIg]. (Left space below) General formula [Ia] -N-NT General formula [Id'] General formula [1f] General formula [If'-General formula [na] General formula [11b] General formula [II f] General formula [ II g] (hereinafter blank) General formula [Idl[11a], [Idl[Id'1[11
R according to dl, [Ie] [IIe] and [11a]
, represents a group capable of hydrogen bonding, -form % formula %] At least one of R2 contains a group capable of hydrogen bonding,
General formula [Ia] ~ [I f'], to [Summer a] [11
R2 of the above-mentioned group capable of hydrogen bonding in g1
and R5 represents a hydrogen atom or a substituent; L represents O or 1; Represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. Note that [tf] [R3 in tf'l Cut
There may be several groups, and in this case, one group may be different from each other. The group capable of hydrogen bonding according to the present invention is a substituent having a monovalent hydrogen atom that forms a hydrogen bond with the nitrogen atom in the bira]loazole ring. Further, among the hydrogen-bonding groups according to the present invention, even more preferable ones are electron-withdrawing substituents.
Typical examples of hydrogen-bonding groups include and μ (Ra, Rh, Rc, Rd, Re and Rf represent a hydrogen atom or a tongue substituent, r represents 0 or 1, q haha 0~
Rf represents an integer of 4, but when q is 2 or more, Rf may be the same or different. - Format % Formula % represents 0.1 or 2, R of general formula [1b] [lIb1
2, P represents 1; otherwise, p represents 1 or 2). Ra, Rh and Rd represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, etc. Rc represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, a carbonyl group, etc. which may be substituted with an alkyl group, an aryl group, etc. Re represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, a carbonyl group, etc. which may be substituted with an alkyl group, an aryl group, etc., and preferably a sulfonyl group, a sulfinyl group, etc. and carbonyl groups. Rf represents a hydrogen atom and a substituent, but the substituent represented by Rf is not particularly limited. As the hydrogen-bonding group according to the present invention, particularly preferred is O, and even more preferred among them is -5O2NHRc
. General formulas [Ia] to [I f'] and/or [11
a] to [lIg], when R,, R, and/or R5 are other than a hydrogen bonding group, this R
1, Ih, and/or R5 represent a hydrogen atom or a substituent, and the substituent is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino,
Examples include multiple groups such as sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl; in addition, halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, sulfonyloxy,
phosphonyl, acyl, carbamoyl, sulfamoyl,
cyano, alkoxy, aryloxy, heterocyclic oxy,
siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio polygroups, and spiro compound residues, Also included are bridged hydrocarbon compound residues and multiple groups such as thioureido, carboxy, hydroxy, mercapto, nitro, sulfo, and the like. Among the groups represented by R1 or R3, the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group, a phenyl group is preferred. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R1 or R2 above. The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred. Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc. Sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc. Phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. Ring; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group ring; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc.; As an ureido group, an alkylureido group, an arylureido group, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group ring; l-tetrazolyl group, 1
-Pyrrolyl group ring; the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5.6-
Tetrahydrobilanyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 5-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-benzothiazoli ruthio group, 2,4-diphenoxy-1,3,5-triazole-6 monothio group, etc.; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group; imide group includes succinimide group, 3-heptadecylcohelic acid imide group, phthalimide group, glutarimide group, etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; Bridged hydrocarbon compound residues include bicyclo[2,2,
1] Hebutan-1-yl, tricyclo[3,3,1,1
37] decane-1-yl, 7.7 [2,2,1]hebutan-1-yl, and the like. In the - formations [Ia] to [I f'] and [IIa] to [IIg] according to the present invention, R1+ R
Among 2+ and/or R3, a particularly preferable group that is not a group capable of hydrogen bonding is an electron-withdrawing group, and this electron-withdrawing group preferably has a substituent constant δ defined by Oammett, but +0 .20 or more substituents, typical examples include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, carbamoyl, phosphoryl, pyrrolyl, tetrazolyl, cyano,
In addition to polygroups such as acyl, acyloxy, carboxyl, oxycarbonyl, and nitro, and halogen atoms, α-halogenated alkyl groups such as trifluoromethyl, α-halogenated alkoxy groups such as trifluoromethoxy, and tetrafluoroaryl groups, Pentafluoroaryl groups, tetrafluoroaryloxy groups, pentafluoroaryloxy groups, etc. are also effective, but among these substituents, particularly preferred electron-withdrawing groups are sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, and carbamoyl substituents. It is the basis. General formula [1a] ~ [I f'l and/or [11
In al~[l1g1, examples of the group that can be separated by reaction with the oxidized product of the color developing agent represented by X include halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy,
Polygroups such as alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, etc. However, a halogen atom is preferred, or a bis-isomer may be formed at the active site via a carbon atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms. -Formula [1a] ~ [I f'l and/or [11
a] to [IIgl, Y represents a hydrogen atom and a substituent, and preferable substituents represented by Y include, for example,
After the compound of the present invention reacts with the oxidized developing agent, it is eliminated from the compound. Groups that can be separated under alkaline conditions and JP-A-56
Examples include substituents that are coupled off by reaction with an oxidized developing agent, as described in No. 133734 and the like. Preferably Y is a hydrogen atom. -Formula [1a] to [I f'] and/or [
11a] to [IIgl, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is preferably represented by the following formula [III]. -Formula [III] CH2-C+, ++)-+X++02+-+x2+1
1111 j12 m2 formula,
R4 represents a hydrogen atom, a carboxy group, or an alkyl group (e.g., methyl group, ethyl group, etc.), and this alkyl group may have a substituent, such as a halogen atom (e.g., a fluorine atom). , chlorine atom, etc.), carboxy group, etc. The carboxy group represented by R4 and the carboxy group of the substituent may form a salt. Jl and Jl each represent two bonding groups, and this
2 As the bonding group, for example, -Nl(Go-. -CONH-1-COO-1-OCO-1-CO-1-
sco-cos-1-〇-1-S-1-5O-1-50
2- etc. xl and x2 each represent a divalent hydrocarbon group, and 2
Examples of the valent hydrocarbon group include an alkylene group, an arylene group, an aralkylene group, an alkylenearylene group, and an arylenealkylene group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and an arylene group. Examples of the aralkylene group include a phenylene group, examples of the aralkylene group include a phenylmethylene group, examples of the alkylene arylene group include a methylenephenylene group, and examples of the arylene alkylene group include a phenylene methylene group. etc. J++ ml, J2+ ff12 are each 0
Or represents 1. Next, typical specific examples of the cyan coupler monomers represented by the formulas [Ia] to [I f'] and/or [IIa] to [IIgl] will be exemplarily described; It is not limited to. (Margin below) 9. 1G. 11゜12゜13゜14゜15゜16゜17゜18゜19゜20゜21゜22゜23゜24゜hs 25゜-N-N 36゜H3 General formulas [Ia] to [I f'] and/or [fla] to [IIg] are described in Japanese Patent Application No. 62-85510, No. 62-85511, No. 82-114838, No. 62-115946, etc. Pyrazoloazole compound and acrylic acid halide, methacrylic acid halide or JP-A-58-120252, JP-A-58-120252, JP-A-5B-'21175 synthesized by the method
It can be synthesized by reaction with an acid halide etc. described in No. 6. Typical synthesis examples of the coupler monomer according to the present invention are shown below. Synthesis Example 1 (Synthesis of Exemplary Coupler Monomer (2)) Mutual-→ Exemplary Coupler Monomer (2) (Synthesis of Mutual) Synthesized a with reference to the method described in Japanese Patent Application No. 85511/1983 30. 6 g (0.1 mol) was dissolved in ift tetrahydrofuran, cooled to below 5°C, and 13.4 g (0.1 mol) of N-chlorosuccinimide was added dropwise. After the addition, tetrahydrofuran was distilled off under reduced pressure, the residue was poured into water, and the precipitated crystals were collected by filtration. Recrystallization using acetonitrile yielded 24.0 g (70!1 b). (Synthesis of Exemplary Coupler Monomer (2))
0,05-t-l), 4.7 g of pyridine (0,01i
-E-le) and 1fflIt of nitrobenzene at 200
In addition to mA of tetrahydrofuran, 5.4 g (0, oa mole) of acrylic acid chloride was added dropwise under water cooling, and after stirring for 1 hour, it was poured into 2 L of water, and the precipitate was collected by filtration. Recrystallization using ethanol gave IO, 2 g (52 zero) of the exemplary coupler monomer (2). Elemental analysis value (, C+sH+sNa Os St Cj!
t) Theoretical value C, 45,63H, 3,83N, 2
1.28 Actual value C, 46,25H, 3,50N,
21.82 Synthesis Example 2 (Synthesis of Exemplary Coupler Monomer (17)) (Synthesis of i) 43.1 g (0.1 mol) of c synthesized with reference to the method described in Japanese Patent Application No. 82-8551θ In the same manner as (mutual synthesis) in Synthesis Example 1, it was reacted with N-chlorohelic acid imide, and the obtained crude crystals were recrystallized using acetonitrile to obtain 28.8 g (an) of Sho. (Synthesis of exemplified coupler monomer (17)) 23.3 g
(0.05 mol), pyridine 4.7 g (0.06 mol)
and nitrobenzene 1 tajL to 200 +afL
In addition to tetrahydrofuran, 6.3 g (0.06 mol) of methacrylic acid chloride was added dropwise under water cooling, and after stirring for 1 hour, it was poured into 2λ water and the precipitate was collected by filtration. Recrystallization from ethanol gave 14.9 g (5B!k) of the exemplary coupler monomer (17). Elemental analysis value (C27H211N703 CJ2+) Theoretical value C, 60,73H, 5,211N, 18.3
6 Actual value C; 61.20 H; 5.19
N; 18.51 The cyan polymer coupler of the present invention is a so-called repeating unit consisting of only one type of monomer represented by the general formulas [1a] to [If'l and/or [Natsu 1a] to [11g1]. It may be a homopolymer or a copolymer combining two or more of the monomers represented by the general formulas [1a] to [I f'] and/or [na] to [IIgl, and furthermore, other monomers may be used. 1 of the comonomers having an ethylenically unsaturated group that can be copolymerized with
It may also be a copolymer consisting of more than one species. The comonomer having an ethylenically unsaturated group capable of forming a copolymer with the monomers represented by the general formulas [Ia] to [I f'] and/or [11al to [IIgl] of the present invention includes acrylic esters. , methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters,
Maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional nitrites, various unsaturated acids, etc. be able to. More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, te
rt-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
Octyl acrylate% tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclo Hexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate , 2-ethoxyethyl acrylate, 2-1so-propoxy acrylate, 2-butoxyethyl acrylate, 2-(
2-methoxyethoxy)ethyl acrylate, 2-(2
-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n
"9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, etc. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N- Ethyl-N
-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ditoxyethyl methacrylate, 2-1so-propoxyethyl Methacrylate, 2-butoxyethyl methacrylate, 2-(2
-methoxyethoxy)ethyl methacrylate, 2-(2
-ethoxyethoxy)ethyl methacrylate, 2-(2
-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added, n=6), allyl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, and the like. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, l-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, vinylbenzoic acid methyl ester, etc. can be mentioned. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propyl methacrylamide, butyl methacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide , N-(2-acetoacetoxyethyl) methacrylamide; Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, furyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether , methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyl oxazolidone. , N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylatrile, etc.; Methylene bisacrylamide, ethylene glycol dimethacrylate, etc.; Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleate, e.g. , monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyalkylsulfonic acid, Acryloyloxypropylsulfonic acid, etc.;
Methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, for example 2-methacrylamido-2 - methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, and acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl- 2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.; sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups, and the like. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Furthermore, other comonomer compounds include U.S. Pat. No. 3,459,790
No. 3,438,708, No. 3.554.98
No. 7, No. 4.215,195, No. 4.247.6
It is possible to use the crosslinked materials described in No. 73, Japanese Patent Application Laid-open No. 57-205735, and the like. Specifically, an example of such a crosslinkable polymer is N-(
2-acetoacetoxyethyl)acrylamide N-(2
-(2-acetoacetoxyethoxy)ethyl)acrylamide and the like. Among these comonomers, acrylic esters and methacrylic esters are preferably used in view of the hydrophilicity and lipophilicity of the comonomers, the copolymerizability of the comonomers, the coloring properties of the produced polymer couplers, and the color tone of the produced dyes. , maleic esters, acrylamide, and methacrylamide. Two or more of these comonomers may be used in combination. 2
Examples of combinations when using more than one species include, for example, n
-butyl acrylate and methyl acrylate, styrene and N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, tart-butyl acrylate and methyl methacrylate, and the like. Further, when forming a copolymer with the monomer represented by the formulas [Ia] to [I f'] and/or [IIal to [11g1] of the present invention and the comonomer, preferably the comonomer is formed by the formula [1a] The repeating unit consisting of monomers represented by ~[I f'l and/or (nal~[ngl) is 10 to 90% by weight of the entire polymer.
It is a case where it is contained, and more preferably a case where it is contained in an amount of 30 to 70% by weight. - Numerically, the polymer coupler is polymerized by an emulsion polymerization method or a solution polymerization method, and the above-mentioned formula [! a]～
Polymers of the present invention having repeating units derived from monomers represented by [■f'] and/or [IIa] to [IIgl can also be polymerized in a similar manner. Emulsion polymerization methods are described in U.S. Pat. 451.1120 can be used. These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the comonomer may be a liquid polymer, which in the case of emulsion polymerization normally acts as a solvent for the immobilized monomer. also works. Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art. Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Further, examples of the polymeric protective colloid include polyvinyl alcohol, hydroxydiethylcellulose, and the like. These protective colloids may be used alone as emulsifiers or in combination with other surfactants.For the types of these active agents and their effects, see Belgisc.
HeChemlsche Industries, 28
．． 16-20 (1963). In order to disperse a lipophilic polymer synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, the lipophilic polymer is first dissolved in an organic solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into a latex form using ultrasonic waves, a colloid mill, etc. A method of dispersing lipophilic polymers in latex form in aqueous gelatin solutions is described in US Pat. No. 3,451,820. Examples of organic solvents that dissolve lipophilic polymers include esters such as methyl acetate, ethyl acetate, propyl acetate, etc.
Alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used. Moreover, these organic solvents can be used alone or in combination of two or more. In producing the cyan polymer coupler according to the present invention, the solvent used for polymerization is preferably one that is a good solvent for the monomer and the polymer to be produced and has low reactivity with the polymerization initiator. Specifically, water, Examples include toluene, alcohol (e.g. methanol, ethanol, 1so-propanol, tert-butanol, etc.) acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, methylene chloride, etc., and these solvents can be used. may be used alone or in combination of two or more. The polymerization temperature is usually in the range of 30 to 120°C, although it is necessary to take into account the type of polymerization initiator, the type of solvent used, etc. Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the cyan polymer coupler of the present invention include those shown below. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, anthenium persulfate, and sodium persulfate.
．． Sodium 4'-azobis-4-cyanovalerate, 2.
Water-soluble azo compounds such as 2'-azobis(2-amidinopropane) hydrochloride and hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'
-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1°1'-azobis(cyclohexanone-1
-carbonitrile), 2.2'-azobisisocyanobutyric acid, dimethyl 2.2'-azobisisobutyrate, 1゜1'-
Azobis (cyclohexanone-1-carbonitrile),
4. Azo compounds such as 4'-azobis-4-cyanovaleric acid, peroxides such as benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, diisopropylberoxydicarbonate, di-t-butyl peroxide, etc. etc. can be mentioned. Among these, preferred are benzoyl peroxide, chlorobenzyl peroxide, lauryl peroxide and the like. These polymerization initiators can be contained in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight, based on the total amount of polymer in the emulsion polymerization method and the solution polymerization method. Furthermore, polymerization methods other than those described above, such as suspension polymerization and bulk polymerization, can also be applied. That is, in the present invention, the above formula [1a] ~
A homopolymer of the monomers represented by [I f'] and/or [na] to [11g1, a copolymer formed by a combination of two or more of the monomers, or a polymer of the monomer and at least one other species. It includes all copolymers made of possible comonomers and is not limited by the synthesis process. Next, the production of the polymer coupler of the present invention will be specifically described below, but the present invention is not limited thereto. Synthesis Example 3 Synthesis of Illustrative Coupler Monomer (2) and Lipophilic Polymer Coupler Latex A of n-butyl acrylate A mixture of Illustrated Coupler Monomer (2) Log, 10 g of n-butyl acrylate, and 120 mft of dioxane was
Stir in a nitrogen stream at 0°C and add 4 mj of dioxane! After adding 0.313 g of azobisisobutyronitrile dissolved in the solution, the mixture was reacted for 6 hours. A dioxane solution was dropped into water 21, and the precipitated solid was collected by filtration, washed with water, and dried to give 18.4 g.
(929 g) of lipophilic polymer coupler was obtained. The copolymer composition of this polymer coupler was determined by elemental analysis to have a coupler monomer (2) content of 51.7%. 10 g of the above polymer coupler was dissolved in 30 mA of ethyl acetate, and a mixed solution of 611 IL of a 10% aqueous solution of sodium lauryl sulfate and 100 mu of a 5wt 0% gelatin aqueous solution was added to this solution and subjected to ultrasonic dispersion. Thereafter, ethyl acetate was removed by vacuum distillation to obtain latex A of the polymer coupler. Synthesis Example 4 Synthesis of exemplified coupler monomer (17) and methyl acrylate into lipophilic polymer coupler latex A mixture of 10 g of exemplified coupler monomer (17), 10 g of methyl acrylate, and 120 ml of dioxane was stirred at 80° C. in a nitrogen stream, After adding 0.38 g of azobisisobutyronitrile dissolved in 4 mJl of dioxane, the mixture was reacted for 6 hours. A dioxane solution was dropped into water ZJZ, and the precipitated solid was collected by filtration, washed with water, and dried.
g (90 polymer couplers were obtained. The copolymer composition of this polymer coupler was determined by elemental analysis to show that the content of coupler monomer (17) was 52.1%. The above polymer coupler was treated in the same manner as in Synthesis Example 3. A polymer coupler latex K was obtained. Using the above coupler monomer, the polymer coupler latex shown in Table 1 was obtained in the same manner as for the copolymer of Synthesis Example 3.4. (The following is a blank space.) Table 1 Table 1 -1 (continued 1) * B^ ;n-butyl acrylate E^;ethyl acrylate M^;methyl acrylate^;n-butyl methacrylate^;methyl methacrylate H^;n-hexyl acrylate EH^;2-ethyl Hexyl acrylate AAM
, acrylamide Sτ ; styrene^^ Niacrylic acid The cyan polymer coupler in the present invention can be used alone or in combination with generally well-known couplers. It may be the same dye image-forming coupler as the cyan polymer coupler of this invention, or it may be a different dye image-forming coupler. Colored couplers with color-correcting effects or development inhibitors, releasing couplers, and couplers in which the product formed by the coupling reaction is colorless can also be used in conjunction with the cyan polymer couplers of the present invention. . Mixable couplers are preferably non-diffusible couplers that have a hydrophobic group called a ballast group in their molecules.
U.S. Patent No. 4.08G, 211, U.S. Patent No. 3,163,6
No. 25, No. 3,451゜820, No. 4.215,
No. 195, British Patent No. 1,247゜688, JP-A-5
No. 7-94752, No. 5B-28745, No. 58-4
2044 and 58-43955, or water-soluble polymer couplers having a sulfonic acid group or a carboxylic acid group, in which case they may be added to the hydrophilic colloid as an alkaline solution. Also good. When the coupler of the present invention is added to a silver halide emulsion, it is usually 0.01 to 2 mol per mol of silver halide,
It is preferably added in an amount of 0.03 to 0.5 mol. When the coupler has an acid group such as sulfonic acid or carboxylic acid, it may be added to the wood-philic colloid as an alkaline solution. The color photosensitive materials of the present invention include, for example, color negative and positive films, and color photographic paper. The photosensitive materials of the present invention, including this color photographic paper,
It may be for a single color or for multiple colors. In a multicolor light-sensitive material, the cyan polymer coupler of the present invention may be contained in any layer, but is preferably contained in a red-sensitive silver halide emulsion layer. Multicolor light-sensitive materials have dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum. Each building block can consist of a single or multiple emulsion layer sensitive to a certain region of the spectrum. The constituent layers of the photosensitive material, including the layers of image-forming units, can be arranged in various orders as is known in the art. A typical multicolor light-sensitive material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers being a cyan polymer of the present invention). ), a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive halide emulsion layer containing at least one yellow coupler. It consists of a yellow dye image-forming structural unit consisting of a silver emulsion layer supported on a support. The photosensitive material can have additional layers such as filter layers, interlayers, protective layers, subbing layers, etc. Silver halide compositions preferably used in the present invention include silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used. In other words, when the silver halide emulsion according to the present invention is used in a color photographic paper, particularly fast developability is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and silver chloride, silver chlorobromide, or silver chloroiodobromide containing at least 1% of silver chloride is particularly preferable. The silver halide emulsion is chemically sensitized by conventional methods. Furthermore, it can be optically sensitized to a desired wavelength range. Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, compounds known as antifoggants or stabilizers in the photographic industry may be added for the purpose of preventing fog during photographic processing and/or keeping photographic performance stable. The color photosensitive material of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet inhibitor, which are commonly used in photosensitive materials,
Antistatic agents, matting agents, surfactants, etc. can be used. Regarding these, for example, Research Disclosure w
-(Research Disclosure) 1
The description in Vol. 78, pp. 22-31 (December 19713) can be referred to. An image can be formed on the color photosensitive material of the present invention by subjecting it to a color development process known in the art. The color light-sensitive material according to the present invention may contain a color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. After color development, the color photosensitive material of the present invention is subjected to a bleaching process and a fixing process. Bleaching treatment may be performed simultaneously with fixing treatment. After the fixing process, a washing process is usually performed. Further, a stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination. [Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 A red-sensitive color photosensitive material sample 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Note that the amount of the compound added is per 112 unless otherwise specified (silver halide is a silver equivalent value). 1st layer: Emulsion layer 1.2 g of gelatin, 0.30 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% silver chloride) and 0 dioctyl phthalate
．． A red-sensitive emulsion layer consisting of 0.45 g of comparative cyan coupler a dissolved in 20 g. 2nd layer: Protective layer Protective layer containing 0.50g of gelatin, and 2 as a hardening agent
．． 4-dichloro-6-hydroxy-3-triazine sodium salt was added at a concentration of 0.017 g per gram of gelatin. Next, Samples 2 to 13 of the present invention were prepared in exactly the same manner as in Sample 1, except that comparative coupler a was replaced with the coupler shown in Table 2 (the amount added was the same molar amount as comparative coupler a). Samples 1 to 13 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step. (Development process) Color development 38℃ 3 minutes 30 seconds bleach fixing
38t 1 minute 30 seconds stabilization treatment/or washing treatment 25°C to 30°C 3 minutes drying 75°C to 80°C 2 minutes The composition of the treatment liquid used in each treatment step is as follows. (Color developer) Benzyl alcohol 15 sj ethylene glycol 15 ts potassium sulfite 2.0 g potassium bromide
0.7g Sodium chloride 0.28 Carbonate
Rium 3
0.0g hydroxylamine sulfate 3.
0g polyphosphoric acid (TPPS) 2.5
g3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2
．． Add 0g water and bind the total volume, p) 110.
Adjust to 20. (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid fi1 3g Ammonium thiosulfate (70% solution) 100m! Ammonium sulfite (40% solution) 27.5mj Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, add water and transfer the total amount to IL.
shall be. (Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g
-Ethylene glycol 10 g
Add water to make IfL. Spectral absorption maximum wavelengths (λ, □) and λ, 1. The reflection density at 1.
The reflection density at 420 nm (Dλ4..) at 0 and the reflection density at this time of 0.5, λ,,ll
The half width (WH), which is the difference between one point on the longer wavelength side and one point on the shorter wavelength side than λ,□, was measured, and the spectral absorption characteristics and color reproducibility were examined. The smaller the value of Dλ4110, the less asymmetric absorption in the green region, and the smaller the value of wH, the sharper the absorption and the better the color reproducibility. In addition, each of the above treated samples was heated at high temperature (60℃, 80%R).
H) The dye image was left in an atmosphere for 14 days, and the heat resistance and moisture resistance of the dye image were examined. The obtained results are also shown in Table 2. However, the heat resistance and humidity resistance of the dye image is expressed as the percentage of dye remaining after the heat resistance and humidity resistance test with respect to the initial density of 1.0. A Model 78 densitometer (manufactured by Konica Corporation) was used. Comparative coupler a CsH+ I(t) 6g Comparative coupler b Table 2 As is clear from the results in Table 2, the samples using the coupler of the present invention and the comparative coupler b had a higher performance than the sample using the comparative coupler a. , both have very small half-widths,
It can be seen that the spectral absorption characteristics are excellent because the asymmetric absorption is small. Furthermore, it can be seen that it has a high dye residual rate, excellent heat resistance and moisture resistance, and is robust. Example 2 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to produce a red-sensitive color reversal photographic material. Unless otherwise specified, the amount of the compound added is per 1 m2 (silver halide is equivalent to silver) 1st layer: Emulsion layer 1.4 g of gelatin, red-sensitive silver chlorobromide emulsion (silver chloride 96 mol%) Contains) 0.5g and dibutyl phthalate 0.2
Comparative coupler a%b and polymeric coupler of the invention E%F% L, OlU, (9,1
A red-sensitive emulsion layer consisting of xlO-'mol). 2nd layer: Protective layer A protective layer containing 0.5 g of gelatin, and 2.0 g as a hardening agent.
4-dichloro-6-hydroxy-3-triazine sodium salt was added at a concentration of 0.017 g per gram of gelatin. The samples obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step. [Reversal process] Process Time Temperature First development 6 minutes 38℃ Water washing 2 minutes 38℃ Incubation
Transfer 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃ fixation 4 minutes 38℃ water
Washing 4 minutes Stable at 38°C 1 minute Normally wet and dry The composition of the drying solution used is as follows. [First developer] Water
700 11R Sodium Tetrapolyphosphate
2g sodium sulfite 20
g Hydroquinone monosulfonate 30 g
Sodium carbonate (monohydrate) 30g l-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g potassium bromide
2.5g potassium thiocyanate
1.2g potassium iodide (0.1% solution)
Z mj add water
1000 mj [reversal liquid] water
700 mR Nitrilotrimethylenephosphonic acid 6Na salt 3g 1st chloride
Tin (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide
5g glacial acetic acid
Add 15 ml water
1000 tnl [color developer] water
700 ml sodium tetrapolyphosphate
2g Sodium sulfite 7g
Tertiary sodium phosphate (decahydrate) 36g Potassium bromide 1g Potassium iodide (0,
1% solution) 90 ml sodium hydroxide 3 g citrazic acid
1.5 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11 g ethylenediamine 3 g Add water
1000 mj [Adjustment liquid] Water
700 mj sodium sulfite
12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 ml Glacial acetic acid
Add 3 ml water
1000 mj [tll white liquor water
600mj! Sodium ethylenediaminetetraacetate (dihydrate) 2.0gEthylenediaminetetraacetate iron (111) ammonium (dihydrate) 120.0
g Potassium bromide 100.0g
Add water and make 1000 yal
!

[Fixer]

water
800 a+j ammonium thiosulfate
ao, og sodium sulfite
5.0g sodium bisulfite 5.
Add 0g water and 1000f
f1i+ [stabilizer] water
800 tnR formalin (37% by weight)
5.0mJ! add water
1000 ttrl Regarding the sample treated above, the spectral absorption maximum wavelength (λ1.M) was determined as in Example 1.
and half width (WH), Dλ4. . was measured. In addition,
For various measurements in Example 2, transmission density was measured using a KD-7R densitometer. As a result, the samples using the coupler of the present invention and the comparative coupler b had a smaller half-width than the sample using the comparative coupler a, and the Dλ420
It can be seen that the color is small, has excellent spectral absorption characteristics, and has good color reproducibility. It can also be seen that the samples using the coupler of the present invention have a significantly improved dye image retention rate and are robust. Example 3 A polymer coupler latex containing 6 g of the polymer coupler of the present invention was added to the residual liquid obtained by centrifuging 500 g of a red-sensitized silver chlorobromide emulsion to remove silver halide crystals to prepare a dispersion. A dispersion of comparative couplers was prepared by heating a mixture of 6 g of each coupler, tricresyl phosphate, and ethyl acetate IBg to 60°C to dissolve it, and then adding this to a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). 1
Mix with 15hu of 5% gelatin aqueous solution containing 5ml,
The mixture was emulsified and dispersed using an ultrasonic disperser, and the dispersion was further distilled under reduced pressure to remove ethyl acetate to obtain a dispersion. To observe the dispersion stability of these cyan couplers, the dispersions were stored in the refrigerator (5°C) for 10 days and then
Keep warm in a warm bath at ℃, and observe crystal precipitation using an optical microscope.
Observations were made immediately after incubation, 10 hours later, and 20 hours later. The results are shown in Table-3. Table 3 *20: No precipitation △; Partial precipitation It was found that a highly stable dispersion can be obtained. [Effects of the Invention] According to the present invention, a clear cyan image with excellent spectral absorption characteristics can be formed using a color photographic material containing a pyrazoloazole type polymer coupler, and the cyan image is resistant to heat and humidity. It is very stable against Further, the coupler has excellent stability of the coupler dispersion even during refrigerated storage. Patent applicant Konica Co., Ltd. Representative patent attorney Miki Nakajima Yu and two others

Claims (1)

[Claims] A pyrazoloazole cyan polymer coupler having at least one hydrogen bondable group at a substitutable position other than the active site.