JPH0577063B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material with improved sensitivity, gradation (γ), and color density. It is about the method. More specifically, 1H-pyrazolo[1,5-b]-1,2,4-triazole and 1H characterized by having a substituted or unsubstituted alkyloxy group, aryloxy group, or heterocyclic oxy group at the 6-position -pyrazolo[5,1-c]-1,2,
In the presence of a 4-triazole magenta coupler,
The present invention relates to a color image forming method in which a silver halide color photographic light-sensitive material is developed with a developer containing an aromatic primary amine. (Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, and the like. It is well known that similar pigments are produced and color images are formed. Among these, 5-pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used to form a magenta image. Hitherto, 5-pyrazolones have been widely used as magenta image-forming couplers and have been studied extensively. However, 5-
Dyes formed from pyrazolone couplers are
It has been known that unnecessary absorption with a yellow component exists around 430 nm, causing color turbidity. Pyrazolobenzimidazole bone core described in UK Patent No. 1047612 as a magenta imaging bone core that reduces this yellow component, US Patent No. 3770447
Indazolone bone core described in No.
Pyrazolo[5,1-c]- described in No. 3725067
A 1,2,4-triazole bone core has been proposed. However, the magenta couplers described in these patents, when dispersed in hydrophilic protective colloids such as gelatin, give unsatisfactory color images when mixed into silver halide emulsions, or The dyes are still unsatisfactory because they have low solubility in solvents, are difficult to synthesize, have relatively low coupling activity in common developers, and have extremely low light fastness. There is something. The inventor of the present invention searched for various new types of magenta color image couplers that do not exhibit sub-absorption near 430 nm, which is the biggest drawback in terms of hue of 5-pyrazolone couplers, and found that they exhibit sub-absorption on the short wavelength side. 1H-pyrazolo[1,5-b]-1,2,4 disclosed in JP-A-59-171956 and U.S. Pat. No. 4,540,654, which has high color image fastness and is easy to synthesize.
-Discovered triazole magenta couplers.
These couplers have excellent color reproduction and are excellent in synthesis, and have the characteristics that by introducing a leaving group into the coupling active position, they can be made into so-called 2-equivalents, and the amount of silver used can be reduced. However, when the coupling-off group (X) is synthetically easy, such as halogen, alkylthio, or arylthio, there is a problem that the sensitivity and gradation (γ) are slightly inferior to 5-pyrazolone magenta couplers. Ta. Therefore, the patent application No. 59-176352
It has been found that a coupler in which X is an aryloxy group as shown in Figure 1 is a means to solve this problem. However, although this aryloxy breakaway coupler solves the above problems,
The synthesis yield is low and it is unsuitable for large-scale synthesis,
The drawback was that it had low stability. Furthermore, the pyrazolotriazole disclosed in the aforementioned US Pat. No. 3,725,067 had similar drawbacks. An object of the present invention is to solve these problems and provide a magenta coupler that exhibits even higher sensitivity and improved gradation (γ). (Means for solving the problem) The above problem is solved in the presence of at least one coupler represented by the general formulas () and ().
The problem was solved by a color image forming method characterized by developing a silver halide photosensitive material with a developer containing an aromatic primary amine. General formula ()

[Formula] In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ represents a hydrogen atom or a substituent. General formula ()

[Formula] In the formula, R ₁ represents the same group as above, and R' ₂ represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a heralocyclic thio group. X represents a coupling-off group linked via a nitrogen atom or a sulfur atom. More specifically, R ₁ is a methyl group, an ethyl group,
Isopropyl group, t-butyl group, trifluoromethyl group, phenylmethyl group, methoxyethyl group,
2-phenoxyethyl group, 2-methylsulfonylethyl group, 2-hydroxyethyl group, 3,3,3
-trifluoropropyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group,
Alkyl groups such as 2-cyanoethyl group, 3-oxobutyl group, or phenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 4-acylaminophenyl group, 4-halogenophenyl group, 4
- Aryl groups such as alkoxyphenyl groups, and heterocyclic groups such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 2-pyridyl, 3-pyridyl, and 4-pyridyl groups represents. R ₂ is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group [e.g., a sulfonamide-substituted alkyl group (sulfonamidomethyl group, 1-sulfonamidoethyl group, 2-sulfonamidoethyl group, -methyl-2-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.), acylamino group-substituted alkyl group, (acylaminomethyl group, 1-acylaminoethyl group, 2-
acylaminoethyl group, 1-methyl-2-acylaminoethyl group, 3-acylaminopropyl group, etc.), sulfonamide-substituted phenyl alkyl group (p-sulfonamidophenylmethyl group, p-sulfonamidophenylethyl group, etc.) , 1-(p-sulfonamidophenyl)ethyl group, p-sulfonamidophenylpropyl group, etc.), acylamino-substituted phenyl alkyl group (p-acylaminophenylmethyl group, p-acylaminophenyl ethyl group, 1-(p-acylaminophenyl)ethyl group,
p-acylaminophenylpropyl group, etc.), alkylsulfonyl-substituted alkyl groups (2-dodecylsulfonylethyl group, 1-methyl-2-pentadecylsulfonylethyl group, octadecylsulfonylpropyl group, etc.), phenylsulfonyl-substituted alkyl group ( Substituted alkyl groups such as 3-(2-butyl-5-t-octylphenylsulfonyl)propyl group, 2-(4-dodecyloxyphenylsulfonyl)ethyl group, etc.), methyl group, ethyl group, hexyl group, dodecyl group [unsubstituted alkyl groups such as], aryl groups (e.g., sulfonamidophenyl group, acylaminophenyl group, alkoxyphenyl group, aryloxyphenyl group, substituted alkylphenyl group, sulfonamide naphthyl group,
Substituted aryl groups such as acylaminonaphthyl groups,
and unsubstituted aryl groups such as phenyl and naphthyl groups), heterocyclic groups (e.g., 2-furyl group, 2-furyl group,
-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecylethoxy group, 2-methanesulfonylethoxy group, etc.) ), aryloxy groups (e.g. phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), acylamino groups (e.g. acetamido group, benzamide group, tetradecaneamide 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)dodecanamide}aniline group, etc.), ureido group (e.g., phenylureido group, methylureido group, N,N dibutylureido 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) group, 2-butoxy-5-
t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
etc.), alkoxycarbonylamino groups (e.g.
methoxycarbonylamino group, tetradecyloxycarbonylamino 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-dodecylcarbamoyl group, N-{3
-(2,4-di-tert-amylphenoxy)propyl}carbamoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N
-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), alkoxycarbonyl group (e.g.
methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), and among these, preferably an alkyl group, an aryl group, an alkylthio group,
It is an arylthio group, more preferably an alkyl group or an aryl group. R′ ₂ is a sulfonamido-substituted alkyl group (e.g., sulfonamidomethyl group, 1-sulfonamidoethyl group, 2-sulfonamidoethyl group, 1-methyl-2-sulfonamidoethyl group, 3-sulfonamidopropyl group, etc.), Acylamino-substituted alkyl groups, (e.g., acylaminomethyl groups, 1-
Acylaminoethyl group, 2-acylaminoethyl group, 1-methyl-2-acylaminoethyl group, 3
-acylaminopropyl group) sulfonamide-substituted phenyl alkyl group (e.g. p-sulfonamidophenylmethyl group, p-sulfonamidophenylethyl group, 1-(p-sulfonamidophenyl)ethyl group, p-sulfone amidophenylpropyl group, etc.), acylamino-substituted phenylalkyl group (e.g. p-acylaminophenylmethyl group, p-acylaminophenylethyl group, 1-
(p-acylaminophenyl) ethyl group, p-acylaminophenylpropyl group, etc.), alkylsulfonyl-substituted alkyl groups (2-dodecylsulfonylethyl group, 1-methyl-2-pentadecylsulfonylethyl group, octadecylsulfonylpropyl group, etc.) substituted alkyl groups such as phenylsulfonyl-substituted alkyl groups (3-(2-butyl-5-t-octylphenylsulfonyl)propyl group, 2-(4-dodecyloxyphenylsulfonylethyl group, etc.)) and unsubstituted alkyl groups such as methyl group, ethyl group, hexyl group, dodecyl group, sulfonamidophenyl group, acylaminophenyl group, alkoxyphenyl group, aryloxyphenyl group, substituted alkylphenyl group, sulfone Substituted aryl groups such as amidonaphthyl group and acylaminonaphthyl group, unsubstituted aryl groups such as phenyl and naphthyl groups, and alkylthio groups (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, 2-butoxy-5-t-octylphenylthio group, 3-pentadecyl phenyl thio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, heterocyclic thio group (e.g., 2-benzothiazolylthio group, 2,4-di-phenoxy-1,3,
5-triazole-6-thio group, 2-pyridylthio group, etc.). Among these, preferred are substituted alkyl groups and substituted aryl groups, and more preferred are substituted alkyl groups. X is a group linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide group, 2,
3,4,5,6-pentafluorobenzamide group, octanesulfonamide 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-benzisothiazolyl 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-tetrazole-1
-yl group, benzimidazolyl group, etc.) or a group linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylphenylthio group, Nylthio group, 4-octanesulfonamidophenylthio group, benzylthio group, 2
-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,
5-tetrazolylthio group, 2-benzothiazolyl group, etc.). When R _{1 ,} R _{2 , R} ' ₂ or
Ethylene group, 1,10-decylene group, -CH ₂ CH ₂ -
O-CH ₂ CH ₂ -, etc.), substituted or unsubstituted phenylene groups (e.g. 1,4-phenylene group, 1,
3-phenylene group,

【formula】

[Formula] etc.), X represents the above monovalent group converted into a divalent group at an appropriate position. When those represented by general formulas () and () are included in the vinyl monomer, the linking group represented by either R ₁ , R ₂ or R′ ₂ is an alkylene group (substituted or unsubstituted alkylene group). , for example, methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), phenylene group (substituted or unsubstituted phenylene group, for example,
1,4-phenylene group, 1,3-phenylene group,

【formula】

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

【formula】

【formula】

[Formula], etc.)). Preferred linking groups include the following. −CH ₂ CH ₂ ,

【formula】

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[Formula] -CH ₂ CH ₂ O - CH ₂ CH ₂ - NHCO-,

[Formula] Note that the vinyl group may have a substituent other than those represented by the general formula (), and preferred substituents include a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group). , ethyl group). Monomers including those represented by general formulas () and () may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers. 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-alkyl acrylic acid (such as methacrylic acid), and these acrylic acids. Derivative esters or amides such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, t-butylacrylate, 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 sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene Chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N
-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together.
Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like. As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. The solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced. The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred. Next, specific examples of typical magenta couplers in the present invention will be shown, but the present invention is not limited thereto.

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【formula】

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[Image Omitted] Next, a method for synthesizing the coupler of the present invention using a general formula will be described. Inventor published 60-197688
Although the method for synthesizing 1H-pyrazolo[1,5-b]-1,2,4-triazole in which the position is a hydrogen atom or an alkyl group has been shown in detail, the coupler of the present invention (general formula ()) can also be Although the starting materials are different, they can be synthesized basically by the same method. The synthesis scheme is shown below.

[Table] (R ₁ , R ₂ , and X have the same meanings as above. R' represents an alkyl group or an aryl group.) The substituent X may be introduced from the beginning as above , X=H, and as described later,
Various substituents X may be introduced after skeleton synthesis. In the case of 1H-pyrazolo[5,1-c]-1,2,4-triazole coupler (general formula ()),
It can be synthesized using the method described in Japanese Patent Publication No. 48-30895 using 3-alkoxy (or aryloxy)-5-hydrazinopyrazole as a starting material. Solution polymerization and emulsion polymerization will be described regarding the synthesis method of polymer couplers. First, solution polymerization can be synthesized by the method described in U.S. Pat. A monomeric coupler containing a non-chromogenic ethylene-like monomer (e.g. acrylic acid, alkyl acrylic acid such as α-chloroacrylic acid, methacrylic acid or an ester or amide derived from such acrylic acid (e.g. acrylamide, n - butylacrylamide, n-butyl methacrylate, methyl methacrylate, ethyl methacrylate, etc.)) in a suitable ratio in a soluble organic solvent (e.g. dioxane, methylcellosolve, etc.)
Dissolve or mix at an appropriate temperature (around 30-100°)
Initiation of polymerization (physical action by ultraviolet rays, high-energy radiation, etc., or chemical action by persulfate, hydrogen peroxide, benzoyl peroxide, etc.)
(initiated by generation of free radicals with an initiator such as azobisalkylonitrile). After the polymerization reaction is completed, extrusion into an organic solvent, concentration,
Alternatively, the polymer can be isolated by pouring into water. In addition, there is a US patent on the emulsion polymerization method.
It can be synthesized by the method described in No. 3370952. A general method for introducing a coupling-off group will be described. (1) Methods for connecting nitrogen atoms There are broadly three methods for connecting nitrogen atoms. The first method is US Pat. No. 3,419,391
Nitrosate the coupling active site with an appropriate nitrosating agent as described in the issue, and reduce it by an appropriate method (e.g., hydrogenation using PD-carbon as a catalyst, using stannous chloride, etc.) (chemical reduction method) and reacting it with various halides as a 7-amino compound, mainly amide compounds can be synthesized. The second method follows the directions described in U.S. Pat. No. 3,725,067, namely; a suitable halogenating agent, e.g.
The 7th position is halogenated with sulfuryl chloride, chlorine gas, bromine, N-chlorosuccinimide, N-bromosuccinimide, etc., and then
45135 using a suitable base catalyst, triethylamine, sodium hydroxide,
A coupler linked to the 7-position with a nitrogen atom can be synthesized by substitution in the presence of zaazabicyclo[2,2,2]octane, anhydrous potassium carbonate, or the like.
Among compounds linked by oxygen atoms, compounds having a phenoxy group at the 7-position can also be synthesized by this method. The third method is an effective method when introducing a 6π or 10π electron system aromatic nitrogen heterocycle at the 7th position,
2 for the 7-halogen compound synthesized by the second method as described in Japanese Patent Publication No. 57-36577.
Add a 6π or 10π electron aromatic nitrogen heterocycle in an amount of more than twice the mole and heat at 50° to 150°C without solvent, or heat at 30°C in an aprotic polar solvent such as dimethyl formaldehyde, sulfolane or hexamethylphosphotriamide. By heating at ~150°, an aromatic nitrogen heterocyclic group connected to the 7-position via a nitrogen atom can be introduced. (2) Method of connecting sulfur atoms A coupler having an aromatic mercapto or heterocyclic mercapto group substituted at the 7-position can be prepared by the method described in U.S. Pat.
It can be synthesized by dissolving a heterocyclic mercaptan and its corresponding disulfide in a halogenated hydrocarbon solvent, making the sulfenyl chloride with chlorine or sulfuryl chloride, and adding it to a 4-equivalent coupler dissolved in an aprotic solvent. US patent for method of introducing alkylmercapto group into 7-position
The method described in No. 4264723, that is, the method of introducing a mercapto group into the coupling active position of the coupler and causing a halide to act on this mercapto group, and the method of S-
A one-step synthesis method using (alkylthio)isothiourea, hydrochloride (or bromine-hydrochloric acid) is effective.

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[Chemical] Trimethyl orthocyanoacetic acid ester ()
(SM Mc Elvain et al., Journal of American Chemical Society)
42g (0.29mole) and hydrazine hydrochloride
After heating 21.8g (0.32mole) in 100ml of methanol under reflux for 20 hours, the solvent was removed using an evaporator.
36.2g of 3-amino-5-methoxypyrazole hydrochloride () was obtained by recrystallization from methanol.
(yield 84%). Melting point 145-150° Nuclear magnetic resonance spectrum (CDC ₃ , spectrum of hydrochloride free) δ 3.80 (3H.S) 4.90 (1H.S) 5.30-6.90 (2-3H.br) () 45.0g () Dissolve 0.3mole) in methanol,
Sodium methoxide 28% methanol solution (SM-
28), and 80.6 g (0.3 mole) of methyl 3-phthalimidopropionimide ester hydrochloride was added thereto, followed by stirring at room temperature for 1 hour. In it, hydroxylamine aqueous solution (hydroxylamine hydrochloride 20.9g (0.3 mole))
SM-28 (prepared from 60.3 ml (0.3 mole)) was added and stirred at room temperature for 3 hours. The precipitated crystals were separated, washed with water and acetonitrile, and dried to obtain 71.1 g (yield: 72%) of (). Melting point 196-199° (decomposed) Nuclear magnetic resonance spectrum (DMSO- _d6 ) δ 2.5-2.8 (2H) 3.70 (3H.S) 3.6-3.9 (2H) 5.39 (2H.br.s.) 7.82 (4H. S) ()72g (0.22mole) in acetonitrile 150ml
A solution of 41.7 g (0.22 mole) of p-toluenesulfonyl chloride dissolved in 50 ml of acetonitrile was added dropwise at room temperature over about 1 hour while stirring. After the dropwise addition, the mixture was stirred for about 30 minutes, and then 20 ml (0.24 mole) of pyridine was added and stirred for about 30 minutes.
The reaction solution was poured into ice water, and the precipitated crystals were separated and washed with acetonitrile. Yield of () 80.0g (yield
75.6%). When 15.8 g (0.33 mole) of this () was heated under reflux in 300 ml of methanol and 2.9 ml (0.036 mole) of pyridine for about 2 hours, crystals were precipitated. The precipitated crystals were separated, washed with methanol, and dried to obtain 7.0 g (68.8% yield) of (). Melting point 225-228° Nuclear magnetic resonance spectrum (DMSO-d ₆ ) δ 3.03 (2H.t, J = 7.0) 3.70 (3H.S) 3.87 (2H.t, J = 7.0) 5.10 (1H.S) 7.80 ( 4H.S) 12.40 (1H.brs) () 40.8g (0.13mole) methanol (200ml)
In solution, 7.9 g (0.16 mole) of hydrazine monohydrate
was added and heated under reflux for about 3 hours. After separating the precipitated crystals, the crystals were made into a methanol solution again, 27.5 ml (mole) of concentrated hydrochloric acid was added, and the mixture was stirred and filtered to remove insoluble crystals (phthalhydrazide). When the liquid was evaporated to dryness, crude crystals of () were obtained. Acetonitrile was added to this and by excessive washing, 29.8g (yield: 89.6%) of () could be obtained. Melting point 165−170° (decomposition) Nuclear magnetic resonance spectrum (DMSO− _d6 ) δ 3.0~3.3 (4H) 3.75 (3H.S) 8.35 (~5H.br) () 5.0g (0.020mole) in dimethylacetamide 50ml Add 9.6 ml of triethylamine at room temperature.
(0.069mole) was added, stirred and cooled with ice water.
A solution of 8.2 g (0.020 mole) of 2-octyloxy-5-t-octylbenzenesulfonyl chloride in acetonitrile was added dropwise. By extracting with ethyl acetate and recrystallizing from a mixed solvent of n-hexane and ethyl acetate, 8.0g (yield 72.4%) of () was obtained.
Obtained. Melting point 170-172° Dissolve 5.6 g (0.0095 mole) of 2-butoxy-5-t-octyl-disulfide in 20 ml of dichloromethane and add 1.3 g of surulyl chloride at room temperature.
(0.0095 mole) was added, stirred for 30 minutes, and the solvent was removed using an evaporator.
5-octylsulfenyl chloride was obtained. Dissolve this again in 10ml of dichloromethane,
The mixture was added to a solution of 10.6 g (0.0189 mole) in DMF (40 ml) at room temperature, stirred at 42-44°C for 1 hour, extracted with ethyl acetate, and dried. Purification was performed by concentrated liquid silica gel column chromatography to obtain 5.6 g (yield 70%) of Exemplary Coupler (1) as a powder. Mass spectrometry (FD) 854 (M ⁺ ) Elemental analysis C H N Calculated value 66.12 8.79 8.21 Analysis value 65.91 8.95 8.08 The magenta color image formed from the magenta coupler used in the present invention is a color image stabilized expressed by the following general formula The light fastness is improved by using it together with the agent. general formula

[Formula] However, R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ ,
R ₁₅ each represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an acylamino group, an alkoxycarbonyl group, or a sulfonamide group, and R ₁₃ represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. Also with _R10
R ₁₁ may be ring-closed with each other to form a 5- or 6-membered ring, and R ₁₀ and R ₁₁ may also be ring-closed to form a methylenedioxy ring. Yet again
R ₁₃ and R ₁₄ may be ring-closed to form a 5-membered hydrocarbon ring. These compounds are described in U.S. Patent No. 3,935,016;
No. 3982944, Specification No. 4254216, JP-A-55-
No. 21004, No. 54-145530, British Patent Publication
No. 2077455, No. 2062888, US Patent
No. 3764337, No. 3432300, No. 3574627, No.
Specification No. 3573050, Japanese Unexamined Patent Application Publication No. 152225/1986, No. 53-
No. 20327, No. 53-17729, Specification No. 55-6321,
British Patent No. 1347556, British Patent Publication No. 2066975, Japanese Patent Publication No. 54-12337, Japanese Patent Publication No. 48-31625,
It also includes compounds described in US Pat. No. 3,700,455 and JP-A-61-90155. A preferred embodiment of the present invention is a silver halide color light-sensitive material containing the coupler of the present invention. The coupler of the present invention may be added to a light-sensitive material or may be used by being added to a color developing bath. The amount added to the photosensitive material is 2×10 ^-3 per mole of silver halide.
moles to 5×10 ⁻¹ moles, preferably 1×10 ⁻² to 5×
10 ^-1 mole, and in the case of a polymer coupler, the amount of the polymer coupler to be added may be adjusted so that the above amount of the coloring portion is included, and when used by adding it to a color developer, it is 0.001 to 0.001 to 1000cc per 1000cc of bath. 0.1 mol, preferably 0.01 to 0.05 mol is suitable. The pyrazoloazole coupler of the present invention can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion, alkaline dispersion, preferably latex dispersion, and more preferably oil-in-water dispersion. It can be mentioned as follows. 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 are described in US Pat. No. 2,322,027 and others. 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 phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphel phosphate,
Tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylene phosphonates, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate,
2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.),
Examples include aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include 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;
West German Patent Application (OLS) No. 2541274 and
It is described in issues such as No. 2541230. In addition to silver chloride and silver bromide, the silver halide emulsions used in the present invention typically include mixed silver halides such as silver chlorobromide, silver chloroiodobromide, and silver iodobromide. The silver halides preferably used in the present invention are silver chloroiodobromide, silver iodochloride, or silver iodobromide, and silver chloride, silver bromide, or silver chlorobromide containing 3 mol % or less of silver iodide. The silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Moreover, they may be mixed. The average grain size of the silver halide grains used in the present invention (in the case of spherical or near-spherical grains, the grain diameter is the grain size, and in the case of cubic grains, the grain size is the ridge length, and is expressed as an average based on the projected area) is preferably 2μ or less and 0.1μ or more, particularly preferably 1μ or less and 0.15μ or more. The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains are within ±40% of the average grain size in terms of grain number or weight can be used in the present invention. can. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use. The silver halide grains used in the present invention may have regular crystal shapes such as cubes, octahedrons, dodecahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical shapes. It may have an irregular crystal form, or it may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains. It may be an emulsion consisting of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains. The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography" by P. Glafkides, Chimie et al.
Physique Photographique (published by Paul Montel)
1967)], “Photographic Emulsion Chemistry” by Duffin [GF
Photograhic Emulsion Chemistry by Duffin
(Focal Press, 1966)], “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
AuthorMaking and Coating Photographic Emulsin
(Focal Press, 1964)]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can 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. 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 present. The emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in Research Disclosure No. 17643 and Research Disclosure No. 18716, and the relevant sections are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the two research disclosures mentioned above, and their locations are shown in the table below.

[Table] Various color couplers can be used in the present invention, and specific examples thereof are described in the patents listed in Research Disclosure (RD) No. 17643, -C to G. There is. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important. Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643,
In addition to the couplers described in the patents listed in Sections -C and D, the following can be preferably used in the present invention: A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. 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. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Application No. 2219197, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density. Examples of the magenta coupler that can be used in combination with the pyrazoloazole coupler in the present invention include indazolone- or cyanoacetyl-based couplers, preferably 5-pyrazolone-based couplers, which have a ballast group and are hydrophobic. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof are U.S. Pat. , same No. 2600788
No. 2908573, No. 3062653, No. 3062653, No.
It is described in No. 3152896 and No. 3936015. Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897. In addition, 5-
Pyrazolone couplers provide high color density. Cyan couplers that can be used in the present invention include:
Hydrophobic, diffusion-resistant naphthol and phenolic couplers include the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. A typical example is the oxygen atom dissociating type two-equivalent naphthol coupler described in the above issue. Specific examples of phenolic couplers include U.S. Patent No. 2369929, U.S. Patent No. 2801171,
It is described in No. 2772162, No. 2895826, etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is a phenol having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan coupler, U.S. Patent No. 2772162, U.S. Patent No. 3758308, U.S. Patent No. 4126396,
No. 4334011, No. 4327173, West German Patent Publication No.
3329729 and European Patent No. 121365, etc., and U.S. Pat. No. 3446622 and European Patent No.
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Japanese Patent Nos. 4333999, 4451559, and 4427767. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570.
Also, European Patent No. 96570 and West German Application No.
Specific examples of yellow, magenta or cyan couplers are described in No. 3234533. The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming 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. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned
The patent couplers described in RD17643, Sections ~F are useful. The color photographic material according to the present invention is as described above.
RD, No. 17643, pages 28-29 and the same, No. 18716.
651 can be developed by the usual methods described in the left column to right column. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment. In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, 2 to 9 countercurrent baths are required.
Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) to adjust the membrane pH (e.g., PH 3 to 8). Typical examples include carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid,
phosphonocarboxylic acids, etc.), bactericidal agents (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners, and other additives. Alternatively, two or more of the same or different target compounds may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane PH regulator after treatment. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. (Examples) The present invention will be explained below using Examples, but the present invention is not limited thereto. Example 1 Comparative compound (a) 9.2g as magenta coupler
(16.8 mmol) to tri(2-ethylhexyl)
20 ml of phosphate and 25 ml of ethyl acetate were added and dissolved by heating, and the mixture was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1.0 g of sodium dodecylbenzenesulfonate and stirred at high temperature to obtain a fine emulsified dispersion. The entire amount of this emulsified dispersion was added to 100 g of silver chlorobromide emulsion (6.5 g of Ag) consisting of 50 mol% Br, and 10 ml of 2% 2,4-dihydroxy-6-chloro-s-triazine sodium salt was added as a hardening agent. Sample 1 was prepared by coating on a paper support laminated with polyethylene on both sides so that the amount of silver coated was 200 mg/m ² , and gelatin was provided on the upper layer of this coated layer. Next, Samples 2 to 26 were prepared in exactly the same manner except that comparative coupler (a) was replaced with various couplers shown in Table 1 below in equimolar amounts. These samples (stored for 14 days at 60°C and 70% RH) were subjected to wedge exposure at 1000C.MS.
The following development treatments were performed. Processing process Temperature Time Developing solution 33℃ 3 minutes 30 seconds Bleach-fixing solution 33℃ 1 minute 30 seconds Water washing 28℃~35℃ 3 minutes Developer solution Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 3g 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 solution Ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 5g Make up to 1000ml with water. PH6.8 The maximum color density (Dmax) of the magenta color image of each sample thus obtained was measured. The results obtained are shown in Table 1.

【table】

【table】

【table】

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

【formula】

[Formula] As is clear from the results in the table above, the R ₁ O group at the 6-position of the pyrazolotriazole ring is an alkoxy group,
Even if it is an aryloxy group or a heterocyclic oxy group, rather than using a coupler in which the leaving group (X) at the 7th position is connected with a halogen atom or an oxygen atom,
It can be seen that color images with a significantly higher maximum color density can be obtained by using a coupler having a group linked by a nitrogen atom or a sulfur atom as X (Samples 7 to 7).
9, 18-26 and samples 1-6, 0-17).

Claims (1)

[Claims] 1. A silver halide photosensitive material is developed with a developer containing an aromatic primary amine in the presence of at least one coupler represented by the general formulas () and (). Color image forming method. General Formula () [Formula] In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ represents a hydrogen atom or a substituent. General Formula () [Formula] In the formula, R ₁ represents the same group as above, and R' ₂ represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, or a heterocyclic thio group. X represents a leaving group linked via a nitrogen atom or a sulfur atom.