JPH043860B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color development. More specifically, it relates to a silver halide color photographic light-sensitive material containing a pyrazoloazole magenta coupler having an aromatic sulfonamide group having an alkoxy group, aryloxy group, or heterocyclic oxy group as a substituent on the aromatic ring. be. (Prior Art) In silver halide color photographic materials, there are many methods using so-called dye-forming couplers, which form dyes by reacting with the oxidation products of light-sensitive silver halide emulsions and aromatic primary amine developing agents. It is well known that these are usually used in combination with yellow couplers, cyan couplers and magenta couplers. Among these, the 5-pyrazolone coupler, which is frequently used as a magenta coupler, has major problems in color reproduction, such as its azomethine dye having sub-absorption near 430 nm and poor end-to-end absorption on the long wavelength side of the absorption spectrum. It was hot. Therefore, to solve this problem, a magenta color image forming coupler has been developed for a long time using British Patent No. 1047612.
Pyrazolobenzimidazole bone cores described in No. 1, and pyrazolotriazole bone cores described in US Pat. Also recently, it was newly described in Japanese Patent Application Laid-Open No. 59-162548.
1H-imidazo[1,2-b]pyrazole skeleton,
1H-pyrazolo[1,5-b][1,2,4]-triazole skeleton described in JP-A No. 59-171956,
1H-pyrazolo[1,5-d]-tetrazole skeleton described in JP-A-60-33552, JP-A-60-33552
1H-pyrazolo[1,5-
b]-pyrazole skeleton has been proposed. However, although this family of couplers has solved the above-mentioned problems regarding hue, the couplers do not change when developed under conditions that generate a sufficient amount of oxidized aromatic primary amine developing agent in the silver halide emulsion layer. Because the conversion rate to azomethine dye (hereinafter referred to as color development efficiency) is low, the maximum color density (hereinafter referred to as color development efficiency) is low.
It was found that there was a problem with a decrease in Dmax (abbreviated as Dmax). Methods for increasing this coloring efficiency include introducing a leaving group into the coupling active position, adding a coloring enhancer, and changing the ballast group to one that matches the coupler skeleton (for example, JP-A No. 58-42045).
Coupler described in ), etc. are known. (Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photosensitive material with improved coloring properties using a pyrazoloazole magenta coupler with improved coloring properties (coloring efficiency). It is to be. A second object of the present invention is to provide a novel high-sensitivity silver halide color photographic light-sensitive material using a pyrazoloazole magenta coupler with improved sensitivity. (Means for solving the problem) In order to achieve the above object, as a result of examining various linking groups and ballast groups, a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support was developed. It was found that this can be achieved by a silver halide color photographic light-sensitive material characterized by containing a pyrazoloazole magenta coupler represented by the general formula []. In the general formula [], R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Z _b and Z _c are −
CH-,

[Formula] or =N-. R ₂ represents a substituent. Furthermore, cases in which R ₁ or X forms a dimer or more multimer are also included. Also, Z _b or
Z _c

[Formula] also includes the case where R ₂ forms a dimer or more multimer. However, at least one of R ₁ , X and R ₂ ,
A group represented by the following general formula [A] is included. General formula [A] In the general formula [A], R ¹² represents an aliphatic group,
n represents 1 or 2. * represents the bonding direction with the pyrazoloazole mother nucleus. R ¹³ represents a substituent, m
represents an integer from 0 to 4. In addition, Z _b and Z _c cannot be =N- at the same time,
Z _b is N=- and at the same time Z _c is

If R ₂ is (L ₁ represents a linear or branched alkylene group having 2 to 5 carbon atoms, R _a represents a monovalent group, and b represents 0 to 5 carbon atoms.
Represents an integer of 4. # represents a bond with the pyrazoloazole core. R ¹⁴ represents an alkylene group, and c is 0
Or represents 1. R ¹² has the same meaning as general formula [A]. ),or (L ₂ represents #-NH- or #-NHCO-,
d represents 0 or 1, R _a represents a monovalent group, b
represents an integer from 0 to 4. # represents a bond with the pyrazoloazole core. R ¹² has the same meaning as general formula [A]. ). Conventionally, couplers having -NHSO ₂ - in the linking group have been disclosed in U.S. Pat. No. 2,698,795,
2710803, etc., and _is newly known as a linking group for acylacetanilide type yellow couplers in U.S. Pat. No. 3,894,876, U.S. Pat.
U.S. patent for naphthol-based cyan coupler
4124396, 4334011, etc., and for 5-pyrazolone magenta couplers,
Special Publication No. 32-7039, Japanese Patent Publication No. 44927, Japanese Patent Publication No. 51-44927, Japanese Patent Publication No.
It is known and described in No. 57-146251. However, there are no known examples of its active application to pyrazoloazole couplers, which is the object of the present invention, and there is no known generally predictable relationship between the effects of the combination of the skeleton and the linking group. It is well known that this phenomenon becomes clear only when synthesized as a coupler and applied to silver halide color light-sensitive materials. This is especially true when the skeleton forming the azomethine dye is different from that conventionally known, and is represented by the general formula [A] substituted with an alkoxy group, an aryloxy group, or a heterocyclic oxy group of the present invention. It is surprising that color development was improved when an aromatic sulfonamide group was introduced as a substituent to the pyrazoloazole magenta coupler represented by the general formula []. In the general formula [], a multimer means 2 molecules in one molecule.
It means a group having three or more groups represented by the general formula [ ], and includes bis-forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [] (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or a homopolymer consisting only of a monomer having a moiety represented by the general formula Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products. The compound represented by the general formula [] is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and has a chemical structure generally referred to as azapentalene. It is becoming. Among the couplers represented by the general formula [], a preferred compound is 1H-imidazo[1,2-b]
Pyrazole, 1H-pyrazolo[5,1-c]
[1,2,4]triazoles, 1H-pyrazolo[1,5-b][1,2,4]triazoles, and 1H-pyrazolo[1,5-a]benzimidazoles, each having the general formula [] [] []
Represented by and [ ]. Among these, preferred are those represented by the general formula [], [] and [], and more preferred is the general formula []
It is expressed as

【formula】

【formula】

【formula】

[Formula] The substituents R ₃ , R ₄ and R ₅ in the general formulas [] to [] are hydrogen atoms, halogen atoms, alkyl groups,
Aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfur group Moylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxy carbonyl group,
represents an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom or sulfur atom and is decoupled. The case where R ₃ , R ₄ , R ₅ or X becomes a divalent group and forms a bis body is also included. Furthermore, when the moiety represented by the general formula [] to [] is present in the vinyl monomer, R ₃ , R ₄ or R ₅ represents a simple bond or a linking group, and the general formula [] The moiety represented by ~[] and the vinyl group are bonded. More specifically, R ₃ , R ₄ and R ₅ are hydrogen atoms,
Halogen atoms (e.g. chlorine atoms, bromine atoms,
), alkyl groups (e.g., methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3-(2,4-di-t-amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenooxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g. phenyl group,
4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group,
2-thienyl group, 2-pyrimidyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group,
-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.),
Heterocyclic oxy groups (e.g., 2-benzimidazolyloxy groups, etc.), acyloxy groups (e.g.,
acetoxy group, hexadecanoyloxy group, etc.),
Carbamoyloxy group (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), Acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2,4
-di-t-amylphenoxy)butyramide group,
γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-{4-(4-hydroxyphenylsulfonyl)phenoxy}decaneamide group, etc.) anilino group (e.g. phenylamino group,
2-chloroanilino group, 2-chloro-5-tetradecanamideanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5-{α-(3-t -butyl-4-hydroxyphenoxy)dodecaneamide}anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group, N,N-
dibutylureido group, etc.), imide group (e.g.
N-succinimide group, 3-benzylhydantoynyl group, 4-(2-ethylhexanoylamino)
phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, -butoxy-5-
t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
), heterocyclic thio groups (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g. , phenoxycarbonylamino group, 2,4-di-tert-
butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5 -t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecyl group) carbamoyl group, N-{3-(2,4-di-tert-amylphenoxy)propyl}carbamoyl group, etc.), acyl group (e.g., acetyl group, (2,4-di-tert-
amylphenoxy)acetyl group, benzoyl group,
etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl group, N,N-dibrobylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group) group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group,
), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl groups (e.g.,
phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), and X is connected through a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxyl group, or an oxygen atom. groups (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,
4-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group,
2-cyanoethoxy group, benzyloxy group, 2-
phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked by nitrogen atoms (e.g. benzenesulfonamide group, N
-Ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,6-pentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N,N
-Diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-
3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoynyl group, 2N-1,1-dioxo-3(2H)-oxo-1,2-benziisothiazolyl group, 2-oxo-1,2-dihydro -1
-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,
3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoynyl group, 1-benzyl-5-hexadecyloxy-3
-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-
(4-propanoylphenylazo group, etc.) groups linked by ionic atoms (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t
-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group,
2-(2-hexanesulfonylethyl)-5-tetr
-octylphenylthio group, benzylthio group, 2
-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,
5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4
-triazolyl-5-thio group, etc.). Here, when X contains a group represented by the general formula [A], it is preferable that it not be directly connected to the pyrazoloazole coupler core (that is, when X is not the general formula [A] itself). When R ₃ , R ₄ , R ₅ or group, 1,10-decylene group, _{-CH2CH2 -} O- _CH2CH2- , etc. ₎ , substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-L ₁ -CONH- group (L ₁ represents a substituted or unsubstituted alkylene group or phenylene group. General formulas [] to []] are included in the vinyl monomer. The linking group represented by R ₃ , R ₄ or R ₅ in the case of
CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. 1,
4-phenylene group, 1,3-phenylene group,

【formula】

[Formula] etc.), -NHCO-, -CONH-, -O-, -OCO- and alkylene groups (e.g.

【formula】

【formula】

[Formula], etc.)). Note that the vinyl group in the vinyl monomer may have a substituent other than those represented by the general formulas [] to []. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms. Examples of 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 (such as methacrylic acid), and derivatives of these acrylic acids. ester or amide (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propylacrylate, n-butylacrylate,
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), methylene dibis acrylamide,
vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, Citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together. Next, the sulfonamide group represented by general formula [A] will be explained in detail. General formula [A] In the general formula [A], R ¹² represents an aliphatic group,
n represents 1 or 2. * represents the bonding direction with the pyrazoloazole mother nucleus. R ¹³ represents a substituent, and m represents an integer up to 0 or 4. Further, substituents bonded adjacent to each other on the benzene ring may bond to each other to form a 5- or 6-membered ring. Among the sulfonamide groups represented by the general formula [A], those in which the -OR ¹² group is bonded to the ortho position of the -NHSO ₂ - group are preferred, and those in which R ¹² is an alkyl group are more preferred. In the present invention, Z _b in the general formula [] is =N-, and at the same time Z _c is

R ₂ in the case of [Formula] refers to R ⁵ in the case of the general formula []. R _a has the same meaning as the substituent for R ¹³ as a monovalent group. To explain in more detail about aliphatic groups, aryl groups, heterocyclic groups and acyl groups, aliphatic groups are:
An aliphatic group having 1 to 36 carbon atoms, including straight-chain and branched alkyl groups, alkenyl groups, aralkyl groups, cycloalkyl groups, alkynylene groups, and cycloalkenyl groups, and these aliphatic groups include R ₃ , R Of the groups described in ₄ and R ₅ , each substituent other than the hydrogen atom may be bonded. The aryl group represents a phenyl group, naphthalene group, etc. having 6 to 40 carbon atoms, and various substituents other than hydrogen atoms among the groups described for R ₂ , R ₄ and R ₅ may be bonded to these. A heterocyclic group represents a 5- to 7-membered ring group containing at least one of 1 to 4 nitrogen atoms, oxygen atoms, and ionic atoms in the ring, and includes, for example, a furyl group,
thienyl group, pyrimidinyl group, imidazolyl group,
Represents a pyrazolyl group, benzothiazolyl group, piperidino group, morpholino group, benzimidazolyl group, triazolyl group, triazine group, etc.
Among the groups described for R ₃ , R ₄ and R ₅ , each substituent other than a hydrogen atom may be bonded. The acyl group represents an acetyl group, a propionyl group, a 2-methylpropionyl group, a benzoyl group, etc. In detail, R ¹³ represents the same as described for R ₃ , R ₄ and R _5. Representative examples of the group represented by the general formula [A] are shown below, but the invention is not limited thereto. Representative examples of the coupler represented by the general formula [] of the present invention are shown below, but the coupler is not limited thereto. The coupler represented by the general formula () of the present invention can be synthesized according to the methods described in the following documents. The compound of general formula () is described in JP-A-59-162548, the compound of general formula () is described in JP-A-47-27411, etc., and the compound of general formula () is described in JP-A-59-162548.
No. 171956, etc., the compound of general formula () is US patented.
3061432, etc., respectively. The coupler represented by the general formula [] used in the present invention is preferably added to a silver halide photographic light-sensitive layer, but can be added to a non-light-sensitive photographic layer depending on the purpose. Examples of the silver halide color photographic light-sensitive material for use in the present invention include color paper, color reversal paper, color negative film, color positive film, etc., and it is particularly preferable to use it for color paper and color reversal paper. The magenta coupler of the present invention and the combination couplers described below can be introduced into the light-sensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. This can be cited as an example. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of 175°C or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents include US Pat. No. 2,322,027, and representative examples are described in later sections. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating. Specific examples of high-boiling organic solvents include phthalate esters (e.g. dibutyl phthalate, di-3,
7-dimethyloctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tri- cyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl phenyl phosphonate, etc.),
ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amyl phenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), anilines (N,N-dibutyl-2-butoxy-5-tert-octylaniline) etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and as auxiliary solvents, the boiling point is about 30°C to about 160°C.
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone 2-ethoxyethyl acetate, and dimethylformamide. The process and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat. No. 4,199,363;
It is described in West German Patent Application No. 2541274 and West German Patent Application No. 2541230. The couplers of the invention are preferably added within the light-sensitive silver halide emulsion layer. The range of its addition amount is 0.003 to 0.5 mol per 1 mol of silver halide, 0.005 to 0.3 mol can be preferably used for color sensitive materials for sound photography, and 0.1 to 0.3 mol can be used for color paper. Are suitable. In addition to the magenta coupler of the present invention, conventional color couplers can be used in combination with the color photosensitive material of the present invention. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of cyan, magenta and yellow couplers that can be used in the present invention are RD17643 (December 1978) -
D, No. 18717 (November 1979). Preferably, these couplers have ballast groups or are polymerized and diffusion resistant. The coupling position is preferably substituted with a leaving group rather than a hydrogen atom. Couplers in which the chromophore has suitable diffusivity, colored couplers, colorless couplers, or couplers which release a development inhibitor or development accelerator upon the coupling reaction can also be used. . A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. Two-equivalent yellow couplers can be preferably used in the present invention,
U.S. Patent No. 3408194, U.S. Patent No. 3447928, U.S. Patent No.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4401752, etc.
58-10739, U.S. Pat. No. 4,022,620;
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers are characterized by the fastness of color-forming dyes, while α-benzoylacetanilide couplers are characterized by good color-forming properties. Examples of magenta couplers that can be used in combination with the present invention include oil-protected indazolone or cyanoacetyl couplers, preferably 5-pyrazolone couplers. The 5-pyrazolone coupler is preferably one in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue of the chromophore and the speed of color development. Representative examples thereof include U.S. Pat. No., same No.
It is described in No. 2600788, No. 2908573, No. 3062653, No. 3152896, No. 3936015, etc. Two equivalents of 5-pyrazolone couplers are preferred, with the leaving group being a nitrogen atom leaving group as described in U.S. Pat. No. 4,310,619 or U.S. Pat.
The arylthio group described in No. 4351897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73636 has high color reactivity. Cyan couplers that can be used in the present invention include:
Oil-protected naphthol-based and phenolic couplers are listed, and U.S. Patent No.
Preferably, the naphthol couplers described in U.S. Pat. No. 4,052,212, U.S. Pat.
Typical examples include highly active 2-equivalent naphthol couplers of the oxygen atom elimination type described in Nos. 4,228,233 and 4,296,200. Specific examples of phenolic couplers are disclosed in U.S. Pat. No. 2,369,929;
It is described in No. 2423730, No. 2772162, No. 2895826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, typical examples of which include the phenolic cyan couplers described in U.S. Pat. No. 3,772,002, U.S. Pat.
2,5-diacylamino-substituted phenolic couplers described in German Patent Publication No. 3758308, No. 4126396, No. 4334011, No. 4327173, West German Patent Publication No. 3329729, and Japanese Patent Application No. 1982-42671, etc., and U.S. patents. No. 3446622, No. 4333999, No. 4451559
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 4,427,767 and the like. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. Yellow-colored magenta couplers described in U.S. Pat.
Typical examples include magenta-colored cyan couplers described in No. 4138258 and British Patent No. 1146368. The color coupler that can be used in combination may also form a dimer or more polymer. Typical examples of polymerized couplers are described in US Pat. No. 3,451,820 and US Pat. No. 4,080,211. Specific examples of polymerized magenta couplers are given in UK Patent No. 2102173 and US Patent No.
Described in No. 4367282. In addition, chromophoric diffusive couplers can be used in combination to improve graininess; examples of such couplers are described in US Patent No. 4366237 and British Patent No. 2125570, and European Patent No.
Specific examples of yellow, magenta and cyan are described in German Patent Application No. 3324533). Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size distribution may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal structures such as cubic or octahedral shapes, or may have irregular crystal structures such as spherical or plate shapes, or may have irregular crystal structures such as spherical or plate shapes. It can also be a composite of shapes. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is described in "Chimie et Physique Photography" by P. Grafkides.
Photographique”, Paul Montel
Montel) (1967), GF Duffin (GF
Duffin, “Photographic Emulsion Chemistry”
Chemistry”, Focal Press
Published by the company (1966), VL Zerichmann (VL
Acidic method, neutral method, ammonia method, etc., and as a method for reacting the soluble silver salt and soluble halogen salt, any one-sided mixing method, simultaneous mixing method, a combination thereof, etc. may be used. A method of formation under an excess of silver ions (so-called back mixing method) can also be used.
One type of simultaneous mixing method is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, for example H. freezer (H.
Frieser), ed.
Die
Grundlagender Photographischen Prozesse
mit Silberhalogeniden”, Akademische Verlagsgesellschaft
Verlagsqesellschaft), (1968) No. 675-734
The method described on page can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments,
Included are holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyrene compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aliphatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, active vinyl compound 1,
3,5-Triacryloyl-hexahydro-s-
triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4
-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Pat.
Aryl group-substituted benzotriazoles described in US Pat. No. 3533794, US Pat. Patent No. 3705805 and the same
cinnamic acid esters as described in U.S. Pat. No. 3,707,375; benzophenones as described in U.S. Pat. No. 3,215,530 and British Patent No. 1,321,355; Molecular compounds can be used. Ultraviolet absorbing fluorescent brighteners described in US Pat. Nos. 3,499,762 and 3,700,455 may also be used. A typical example of a UV absorber is RD24239 (1984
(June 2013), etc. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful flexible supports include:
These include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, and polycarbonate, and papers coated or laminated with baryta layers or α-olefin polymers (e.g., polyethylene, polypropylene), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. When using these supports for reflective materials,
It is preferable to add a white pigment to the support or laminate layer. Examples of white pigments include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate. Particularly useful. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. When these supports are used in reflective materials, a hydrophilic colloid layer containing a white pigment at a high density can be further provided between the support and the emulsion layer to improve the whiteness and sharpness of photographic images. In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, and sharpness can be achieved. In addition to improving the optical clarity, a photographic image with particularly excellent saturation and depiction of dark areas can be obtained, which is particularly preferable. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as raw materials for the synthetic resin film, and barium sulfate and titanium oxide are particularly useful as white pigments. In addition to the above, the color photographic material of the present invention may optionally contain various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc. An example can be found in Research Disclosure 17643. Furthermore, in some cases, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, or silver bromide emulsion)
may be added. The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, 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, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-
Representative examples include amino-3-methyl-N-ethyl-N-β-methoxyethylaniline. The color developing solution contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, and as described in OLS No. 2,622,950 It may also contain antioxidants and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, manganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. It may be washed with water after color development or bleach-fixing treatment. Color development can be carried out at any temperature between 18°C and 55°C. Color development is preferably carried out at 30°C or higher, particularly preferably at 35°C or higher. The development time is preferably as short as about 3 and a half minutes to about 1 minute. For continuous development processing, liquid replenishment is preferred, and 330 c.c. to 160 c.c., preferably 100 c.c. or less, of the liquid is replenished per square meter of processing area. The amount of benzyl alcohol in the developer is preferably 5 ml or less. Bleach-fixing can be carried out at any temperature from 18°C to 50°C, but preferably 30°C or higher. When the temperature is 35°C or higher, the processing time can be reduced to 1 minute or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and washing can be done within 1 minute using a stabilizing bath. In addition to deterioration due to light, heat, or temperature, the developed colorant also deteriorates and fades due to mold during storage.Cyan images are particularly susceptible to deterioration due to mold, and it is therefore preferable to use a fungicide. Specific examples of antifungal agents include 2 as described in JP-A-57-157244.
-There are thiazolylbenzimidazoles. The antifungal agent may be built into the photosensitive material, or may be added externally during the development process, or may be added at any process if it coexists with the processed photosensitive material. (Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Example 1 To 8.3 g of Exemplified Compound (M-7), 16.6 ml of tri(2-ethylhexyl) phosphate and 25 ml of ethyl acetate were added.
ml and heated to dissolve. Meanwhile, 10g gelatin,
The above coupler solution was added to 10 ml of an aqueous solution containing 1.0 g of sodium dodecylbenzenesulfonate, and a fine emulsified dispersion of the coupler solution was prepared by high-speed mechanical stirring. The total amount of this emulsified dispersion is Br50
In addition to 100 g of silver chlorobromide emulsion containing mol% (containing 6.5 g of Ag), 10 ml of 2% 2.4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardening agent, resulting in a coating weight of 200 mg of silver. /m ² on a paper support laminated with polyethylene on both sides, and a gelatin layer was coated on top of this coated layer to prepare a sample. This is designated as sample A. Next, exemplified compound (M-7) (M-9) 8.1
g, (M-33), 8.3 g, and the same tri(2-ethylhexyl) phosphate as above, respectively.
An emulsified dispersion was prepared in the same manner as above by adding 16.2 ml, 16.6 ml, 17.6 ml, and 25 ml of ethyl acetate.
Ag coated on the same support using the same amount of the same emulsion
Samples were prepared by applying the same amount.
These samples are referred to as samples B and C, respectively. Furthermore, as a comparative sample, Comparative Compound 1 shown below
17.8 ml of tri(2-ethylhexyl) phosphate to 8.8 g of Compound 2 and 10.3 g of Comparative Compound 2,
A similar sample was prepared using the method described above by adding 20.6 ml and 25 ml of ethyl acetate. These samples are referred to as comparative samples 1 and 2, respectively. These samples A, B, C and comparative samples 1 and 2
A wedge exposure of 1000 C.MS was applied and the sample was 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 Hydroxyamine sulfate 2g 4-Amino-3-methyl-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/Vol%)
150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make 1000ml with water PH6.8 Processing process Temperature Time Developing solution 33℃ 3 minutes 30 seconds Bleach-fix solution 33℃ 1 minute 30 seconds Water Washing 28~ 35°C for 3 minutes The magenta color images of each sample thus obtained had good hue and high saturation.
When the photographic characteristics of these color images were measured, the following results were obtained.

[Table] As a result, it was found that the coupler of the present invention exhibited excellent characteristics in terms of sensitivity, gradation, and variation in maximum density. This is considered to be due to the fact that coupling activity and coloring efficiency are increased by introducing the sulfonamide group of the present invention. Example 2 Color photographic materials E, F, G, H and I were created. At this time, the composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was a solution prepared according to Example 1. These samples E to I were attached with a BGR three-color separation filter, exposed to light in exactly the same manner as in Example 1, and processed. The photographic characteristic values obtained are shown in the table.

【table】

【table】

[Table]
These results demonstrate that the coupler of the present invention exhibits excellent photographic properties even in multilayer samples. Example 3 An emulsified dispersion in which 7.3 g of the photofading inhibitor shown below was added to Samples E to H created in Example 2 and the magenta coupler used in the third layer of Example 2 was used. However, B-G was added to samples I to L, which had the same composition in other respects.
A three-color separation filter of -R was attached, and the exposure and processing described in Example 1 were carried out to obtain various colored images. These colored images were exposed to light for 4 weeks using a fluorescent lamp bleacher (15,000 lux), and a light fastness test of the magenta dye image was conducted. The results are shown in the table.

[Table] Zenta concentration values.
From these results, it was found that the coupler of the present invention has excellent color image fastness to light, and that the fastness can be improved by using a certain kind of photofading inhibitor. In addition, under high temperature of 100℃,
The color image fastness test under high temperature and high humidity conditions of 60℃ and 90% RH showed almost no fading, and there was no staining of the uncolored area after fading due to residual coupler, and it has excellent properties. It was found that the coupler has a Example 4 Exemplary compound (M-7) was prepared in the same manner as in Example 1.
Samples M to Q were prepared by replacing them with equimolar amounts of the couplers listed in the table, and dissolving and coating them in the same manner as sample A. They were exposed and developed in the same manner, and evaluated in the same manner. Note that the relative sensitivity was expressed using Comparative Sample 1 in Example 1 as a reference (100).

[Table] Represents the relative value of exposure. The smaller the value, the lower the exposure and the higher the sensitivity.
Thus, it can be seen that the pyrazoloazole magenta coupler of the present application exhibits superior photographic properties in terms of relative sensitivity, gradation, and maximum sensitivity compared to the comparative pyrazoloazole magenta coupler. (Effects of the Invention) As can be seen from the results of Examples 1 and 2, the coupler of the present invention has excellent sensitivity, gradation, and color development (maximum density) in both single-layer and multi-layer systems. . Furthermore, the results of Example 3 show that the photosensitive material using the coupler of the present invention has excellent light stability of color images. Furthermore, when used in combination with the photofading inhibitor shown in Example 3, the photostability is further improved. In Examples 1 to 3, among the couplers of the present invention, those having a coupler core of the general formula [], and in the general formula [A], the R ¹² O- group is substituted at the ortho position of the sulfonamide group. It can be seen that those having this structure exhibit particularly good photographic properties. Furthermore, in the general formula [A], the products in which the R ¹² O- group is substituted in the ortho position of the sulfonamide group generally exhibit better color development than the products in which the sulfonamide group is substituted in the para position.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, characterized by containing a pyrazoloazole magenta coupler represented by the general formula []. Silver halide color photographic material. General formula [] In the general formula [], R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Z _b and Z _c are −
Represents CH-, [Formula] or =N-. R ₂ represents a substituent. Furthermore, cases in which R ₁ or X forms a dimer or more multimer are also included. Also, Z _b or
When Z _c is [Formula], it also includes the case where R ₂ forms a dimer or more multimer. However, at least one of R ₁ , X and R ₂ ,
A group represented by the following general formula [A] is included. General formula [A] In the general formula [A], R ¹² represents an aliphatic group,
n represents 1 or 2. * represents the bonding direction with the pyrazoloazole mother nucleus. R ¹³ represents a substituent, m
represents an integer from 0 to 4. In addition, Z _b and Z _c cannot be =N- at the same time,
If Z _b is =N- and at the same time Z _c is [Formula], then R ₂ is (L ₁ represents a linear or branched alkylene group having 2 to 5 carbon atoms, R _a represents a monovalent group, and b represents 0 to 5 carbon atoms.
Represents an integer of 4. # represents a bond with the pyrazoloazole core. R ¹⁴ represents an alkylene group, and c is 0
Or represents 1. R ¹² has the same meaning as general formula [A]. ),or (L ₂ represents #-NH- or #-NHCO-,
d represents 0 or 1, R _a represents a monovalent group, b
represents an integer from 0 to 4. # represents a bond with the pyrazoloazole core. R ¹² has the same meaning as general formula [A]. ).