JPH0616160B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in color reproduction, sensitivity and processing characteristics. .

(Prior Art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine type color developing agent and the coupler react to give indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and similar dyes form and form color images.

Most of the 5-pyrazolones that have been widely put into practical use as magenta image-forming couplers and have been studied so far. The 5-pyrazolone coupler is excellent in dye forming speed and efficiency, and the formed azomethine dye is excellent in fastness to light and heat, but has absorption of a yellow component around 430 nm which is not preferable as a magenta dye. It was known that this is the cause of color turbidity.

As a magenta color image-forming bone nucleus that reduces this yellow component, a pyrazolobenzimidazole bone nucleus described in British Patent No. 1,047,612 and US Pat. No. 3,72.
5,067, the pyrazolotriazole bone nucleus, US Pat. No. 4,500,630, the pyrazoloimidazole bone nucleus, JP-A-60-43659, the pyrazolopyrazole bone nucleus, and Europe. Patent No. 119,860A
The pyrazolotriazole bone nucleus described in No. 1 was developed.

The dyes formed by these are preferable in comparison with those formed by the conventional 5-pyrazolones in terms of absorption of an unnecessary yellow component, and the long-wavelength side of the absorption spectrum. It is also a preferable coupler in terms of color reproduction, in that the absorption of R becomes zero.

(Problems to be Solved by the Invention) However, the present inventors have found that these pyrazoloazole couplers have the above-mentioned excellent points, but at the same time have the unfavorable properties described below. .

That is, when these couplers are made to coexist with a silver halide which is an oxidizing agent of an aromatic primary amine type developing agent necessary for the color forming reaction, more specifically, an emulsion dispersion of these couplers and a silver halide are more specifically described. When a coated product was prepared by mixing it with an emulsion and examining its photographic properties, the silver halide emulsion used did not exhibit the original sensitivity, gradation, and fog, and some emulsions were sensitized or desensitized. And the color density decreases again. This is, for example, 5-
This can be confirmed by making a coated product in which a pyrazolone-based coupler is incorporated under the same conditions and comparing the result with color development or black and white development. It is also possible to understand a part of the phenomenon by preparing a coated product containing only a silver halide emulsion to which no coupler is added and comparing the result with black and white development.

Originally, the couplers used in the silver halide color photographic light-sensitive material exert any action on the silver halide emulsion except for the couplers which should have a special function such as a development inhibitor releasing coupler or a development accelerator releasing coupler. In particular, it is not desirable to exert an effect on the photosensitizing process to cause a sensitizing or desensitizing effect.

It has been found that a 5-pyrazolone coupler which has been widely put to practical use as a magenta color image-forming coupler has almost no effect on such a silver halide and a pyrazoloazole-based coupler has a widespread effect.

The pyrazoloazole coupler is a coupler having a pyrazolobenzimidazole ring, a pyrazolotriazole ring, and the like. The compounds having these residues have stronger interaction with silver ions or silver halides than the compounds having 5-pyrazolone residues, which have been widely used as magenta couplers in the past, that is, the action of complex formation or adsorption. We have confirmed that It was also confirmed that such interaction causes a feeling of increase / decrease in emulsion and a decrease in color development.

When a sample prepared by coating a silver halide emulsion and a pyrazoloazole coupler on a support was prepared and examined for the change in interaction due to the halogen species of the silver halide emulsion, it was found that more color was developed in the silver chloride emulsion than in the silver bromide emulsion. It has been found that it is easy to cause a decrease in On the contrary, it was also found that a silver iodobromide emulsion containing silver iodide is less likely to cause a decrease in color development than a silver bromide emulsion or a silver chlorobromide emulsion. That is, in the silver chlorobromide-based emulsion, the interaction with the pyrazoloazole-based coupler for the reduction of the color developability is larger than in the silver iodobromide-based emulsion, and in the light-sensitive material using the silver chlorobromide emulsion, It was even more difficult to introduce an azole coupler.

As one means for solving such a problem, Japanese Patent Application No. 60
No. 162,874 discloses a method of adjusting the pH of a coating film. Although this method is highly effective in breaking the above-mentioned interaction, it has the following inadequacies. That is, the pH of the coating film
Even if it is possible to cut off the interaction in the state of the coating film as it is, it is necessary to go through a developing process for the coating film to develop color, and a pH value of about 9 to 12 is usually required. By immersing in the developing solution shown, p in the film
That is, the H value greatly increases, and a new interaction occurs in the treatment liquid. This interaction is also great in silver chlorobromide.

In any case, it is important to cut off the action on such silver halide, especially silver chlorobromide, and improvement is expected.

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material excellent in color reproducibility, sensitivity and color density.

A second object of the present invention is to provide a silver halide photographic material containing a pyrazoloazole-based coupler and capable of obtaining a highly sensitive and sufficient color density.

(Means for Solving the Problem) The object of the present invention is achieved by a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a pyrazoloazole coupler represented by the general formula [I] on a support. Was given.

General formula [I] In the general formula [I], R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Za is methine, substituted methine, = N- or -NH-
Represents Zb and Zc are also methine, substituted methine, = N-
Or -NH-, but at least one of Zb and Zc is a substituent. A substituted methine having When Zb is the above-mentioned substituted methine, one of Za and Zc is -NH- and the other is either methine, substituted methine or = N-.
When Zc is the above-mentioned substituted methine, Za is -NH- and Zb is methine, substituted methine or = N-.
R ₂ represents either an alkyl group or a halogen atom. R ₃ and R ₄ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group. , Acylamino group, anilino group, amino group, ureido group, imide group, sulfamoylamino group,
Carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group,
It represents an aryloxycarbonylamino group, a sulfonamide group, a carboxyl group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

Among the pyrazoloazole-based magenta couplers represented by the general formula [I], preferred are the following general formulas [II] to [V
I].

R ₂ may be a linear alkyl group or a branched alkyl group, and examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group,
Examples thereof include eicosyl group, cyclopentyl group and cyclohexyl group. These alkyl groups and the following alkyl groups, substituents such as alkoxy groups and aryl groups may further have one or more substituents.
For example, halogen atom (for example, fluorine atom, chlorine atom,
Etc.), alkyl groups (for example, methyl group, ethyl group, propyl group, 2,2-dimethylpropyl group, n-butyl group,
t-butyl group, trifluoromethyl group, tridecyl group,
3- (2,4-di-t-amylphenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.) , An alkenyl group (eg, vinyl group, etc.), an alkynyl group (eg,
1-propynyl group, etc.), aryl group (for example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group,
Etc.), a heterocyclic group (for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
Etc.), cyano group, hydroxyl group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group). Group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-
Benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group,
Etc.), carbamoyloxy group (eg, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, Etc.), acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-hydroxyphenoxy)) Butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (eg, phenylamino group, 2
-Chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α- (3-t- Butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), amino group (eg, ethylamino group, dimethylamino group, methyloctylamino group, etc.), ureido group (eg, phenylureido group, methylureido group) , N, N-dibutylureido group, etc.), imide group (for example, N-succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino Group (for example, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc. An alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group, etc.), An arylthio group (for example, a phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
Etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, , A phenoxycarbonylamino group,
2,4-di-tert-butylphenoxycarbonylamino group, etc., sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group,
Octadecanesulfonamide group, 2-methoxy-5-t
-Butylbenzenesulfonamide group, etc.), carboxyl group, carbamoyl group (for example, 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.), acyl group (for example, acetyl group, 2,4-di-tert-amylphenoxyacetyl group, benzoyl group, etc.), sulfamoyl group (for example, N-ethylsulfur) Humamoyl group, N, N-dipropylsulfamoyl group,
N- (2-dodecyloxyethyl) sulfamoyl group,
N-ethyl-N-dodecylsulfamoyl group, N, N-
Diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, dodecylsulfinyl group, Phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group,
3-pentadecyloxy-carbonyl group, etc.) and the like. Further, examples of R ₂ include a halogen atom.
R ₃ and R ₄ are a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group. Group, acylamino group, anilino group, amino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, a carboxyl group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. More specifically, R ₃ and R ₄ are halogen atoms (eg, fluorine atom, chlorine atom, etc.), alkyl groups (eg, methyl group, ethyl group, propyl group, 2,2-
Dimethylpropyl group, n-butyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3- (2,4-di-t-amylphenoxy) propyl group, allyl group, 2-
Dodecyloxyethyl group, 3-phenoxypropyl group,
2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc., aryl group (for example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group) ,
Etc.), a heterocyclic group (for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
Etc.), cyano group, hydroxyl group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group). Group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-
Benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group,
Etc.), carbamoyloxy group (eg, N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, Etc.), acylamino group (for example, acetamide group, benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-hydroxyphenoxy)) Butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (eg, phenylamino group, 2
-Chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α- (3-t- Butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), amino group (eg, ethylamino group, dimethylamino group, methyloctylamino group, etc.), ureido group (eg, phenylureido group, methylureido group) , N, N-dibutylureido group, etc.), imide group (for example, N-succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino Group (for example, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc. An alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group, etc.), An arylthio group (for example, a phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
Etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, , A phenoxycarbonylamino group,
2,4-di-tert-butylphenoxycarbonylamino group, etc., sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group) Group, 2-methoxy-5-t-butylbenzenesulfonamide group, etc.), carboxyl group, carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl)) Carbamoyl group, N-methyl-N-
Dodecylcarbamoyl group, N- {3- (2,4-di-t
ert-amylphenoxy) propyl} carbamoyl group, etc.), an acyl group (eg, acetyl group, 2,4-di-tert-amylphenoxyacetyl group, benzoyl group, etc.), sulfamoyl group (eg, N-ethylsulfur) Humamoyl group, N, N-dipropylsulfamoyl group,
N- (2-dodecyloxyethyl) sulfamoyl group,
N-ethyl-N-dodecylsulfamoyl group, N, N-
Diethylsulfamoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, dodecylsulfinyl group, Phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group,
3-pentadecyloxy-carbonyl group, etc.).

In the general formulas [III], [IV] and [VI], R ₅ represents a hydrogen atom or a substituent, and the substituent is the R described above.
₃ and R ₄ .

In the general formulas [I] and [II] to [VI], R ₁ represents a hydrogen atom or a substituent, and the substituent is R ₂ as described above.
And those represented by R ₃ and R ₄ , May be represented by. Here, R ₆ is a substituent represented by R ₂ , and is the same as described above. R ₇ and R ₈ are the substituents represented by R ₃ and R ₄ , and are the same as those described above. However, R ₆ ,
R ₇ and R ₈ are different from R ₂ , R ₃ and R ₄ , and only one of them may have a hydrogen atom. In the present invention, R
₁ is Is more preferable, and it is most preferable that none of R ₆ , R ₇ and R ₈ is a hydrogen atom.

Particularly in a silver halide containing 10 mol% or more of silver chloride, R ₁ is Good results are obtained when

In silver bromide, especially silver bromide containing silver iodide, R ₁ is not always If not, it shows relatively good performance.

Further, couplers represented by formulas [II] and [V] are particularly preferable in terms of color developability, hue, effects of the present invention and the like.

Specific examples of typical magenta couplers according to the present invention are shown below, but the present invention is not limited thereto.

M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 M-11 M-12 M-13 M-14 M-15 M-16 M-17 M-18 M-19 M-20 M-22 M-23 M-24 M-25 M-26 M-27 M-28 M-29 The coupler of the present invention can be synthesized by applying the methods described in JP-A-60-190779 and JP-A-60-197688. A synthesis example is shown below.

<Synthesis Example> (Synthesis of Exemplified Compound M-1) 97 g of 3-amino-5-methylpyrazole and 297 g of methyl 2,2-dimethyl-3-phthalimidopropionimidate are stirred at room temperature in methanol for about 1 hour. ,
70g of hydroxylamine hydrochloride and 8 parts of sodium acetate
2 g of a mixed aqueous solution was added, and the mixture was heated under reflux for about 5 hours. The reaction solution was poured into water and the precipitated N- [3- (2H-5-methylpyrazolyl)]-2,2-dimethyl-3-phthalimidopropanamide oxime was separated and washed with a 1: 1 mixed solvent of acetonitrile and water. did. Yield 174g (Yield 51
%), Melting point 110-113 ° C. 100 g of this amidoxime is added to 700 ml of acetonitrile.
A solution of 56 g of p-toluenesulfonyl chloride in acetonitrile was slowly added dropwise while stirring at room temperature. After dropping, 23.5 ml of pyridine was added, and the mixture was further stirred for 1 hour. Then, it was poured into ice water 2, and the precipitated crystals were separated and washed with a 1: 2 mixed solvent of acetonitrile and water. The crystals were added to methanol 1 without drying, 22 ml of pyridine was added, and the mixture was heated under reflux for about 2 hours. After that, methanol was distilled off under reduced pressure, the solution was concentrated to about 200 ml, poured into about 500 ml of water, and stirred for a while. Separate the precipitated crystals, wash with acetonitrile,
By drying, 6-methyl-2 (2,2-dimethyl-2-phthalimidoethyl) -1H-pyrazolo [1,5
-B] -1,2,4-triazole 66 g (yield 70
%) Was obtained. Melting point 197-199 ° C. 50 g of this pyrazolotriazole are added to 100 ml of methanol.
Then, 9 ml of 85% hydradihydrate was added and the mixture was heated under reflux for about 2 hours. 100 ml of water and 20 ml of concentrated hydrochloric acid were added to this solution, the precipitated phthalhydrazide was separated, the liquid was concentrated, and the residue was recrystallized from ethanol to give 6-methyl-2- (1,1-dimethyl-2). -Aminoethyl)-
31 g (yield 75%) of 1H-pyrazolo [1,5-b] -1,2,4-triazole dihydrochloride was obtained. Melting point ~ 1
15 ° C (in sealed tube).

30 g of this hydrochloride was dissolved in 60 ml of dimethylacetamide, 15.7 ml of triethylamine was added, and the mixture was cooled with ice water and well stirred. An acetonitrile solution of 47 g of 5-t-octyl-2-n-octyloxybenzenesulfonyl chloride was added dropwise thereto. The reaction solution was poured into water and extracted three times with ethyl acetate. The extract was dried over magnesium sulfate and then dried under reduced pressure. The obtained solid was recrystallized from a mixed solvent of n-hexane and ethyl acetate to give 6-methyl-2- {1,1-dimethyl-2 (5-t-octyl-2-n-octylbenzenesulfone. Amido) ethyl}
It was possible to obtain 48.5 g (yield 75%) of -1H-pyrazolo [1,5-b] -1,2,4-triazole.
Melting point 130-140 ° C. 30 g of this pyrazolotriazole was added to dichloromethane 40
Dissolve in ml, and then at room temperature, N-chlorosuccinimide 7.0
g and stirred, and after about 30 minutes, the reaction solution was washed twice with water and once with saturated saline, dried over magnesium sulfate, concentrated to dryness, and reconstituted from a mixed solvent of n-hexane and ethyl acetate. 28.6 g of Exemplified Compound (M-1) by crystallization
(Yield 90%) could be obtained. Melting point 115-117
C. Other exemplified compounds could also be synthesized by combining the 3-amino-5-substituted pyrazole and methyl imidate hydrochloride having a substituent capable of deriving the desired coupler, and using the above method.

The coupler of the present invention represented by the general formula [I] contains 1 × 10 ⁻³ mol to 1 mol per mol of silver halide present in the same layer.
It is added to the emulsion layer in a molar ratio of preferably 5 × 10 ^{-2 to} 5 × 10 ^-1 mol. It is also possible to add two or more couplers of the present invention to the same emulsion layer.

In the present invention, cyan and yellow couplers can be used in addition to the magenta coupler.

Typical of these are naphthol or phenolic compounds and open or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers that can be used in the present invention are disclosed in Research Disclosure (RD) 17643 (December 1978), Section VII-D and Patent No. 18717 (November 1979). It is described in.

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The two-equivalent color coupler in which the coupling active position is substituted with a leaving group can reduce the coated silver amount, as compared with the four-equivalent color coupler in which the hydrogen atom is a hydrogen atom. It is also possible to use couplers in which the color forming dye has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,002, a phenol cyan coupler having an alkyl group of ethyl group or more at the meta position of the phenol nucleus, US Pat. Nos. 2,772,162 and 3,
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 58-.
2,5-diacylamino-substituted phenol couplers described in US Pat. No. 4,2671, and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include phenol couplers having an acylamino group at the position.

Various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the photosensitive layer in order to satisfy the properties required for the light-sensitive material, or two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler or 0. 002 to 0.3 mol.

The silver halide emulsion used in the present invention is usually prepared by adding an aqueous silver salt solution (eg silver nitrate) solution and a water-soluble halogen salt solution (eg potassium bromide, sodium chloride alone or a mixture thereof) to a water-soluble polymer such as gelatin. It is manufactured by mixing in the presence of a solution. The silver halide thus produced is typically silver chloride, pure silver chloride, pure silver bromide, or those containing some silver iodide. The silver halide preferably used in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide containing 3 mol% or less of silver iodide. More preferable is silver chlorobromide having a silver chloride ratio of 5 mol% or more. The silver halide grains may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed. For example, in the case of silver chlorobromide grains having different phases, it may be a grain having a nucleus or a single or plural layers richer in silver bromide than the average halogen composition. Further, it may be a grain having a nucleus rich in silver chloride from the average halogen composition or a single or plural layers in the grain. The coupler of the present invention is more advantageous than the other pyrazoloazole couplers in that the gradation does not become softer. It has less silver iodide and less chlorobromide content. This is the case for silver emulsion. Average grain size of silver halide grains (the grain diameter is the grain size for spherical or near-sphere grains, and the ridge length is the grain size for cubic grains).
Is preferably 2 μ or less and 0.1 μ or more, and particularly preferably 1 μ or less and 0.15 μ or more. The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a narrow grain size distribution such that 90% or more, particularly 95% or more of all grains fall within ± 40% of the average grain size in terms of number of grains or weight can be used in the present invention. it can. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The shape of the silver halide grains used in the present invention may have a crystal such as a cube, an octahedron, a dodecahedron and a tetradecahedron, and an irregular shape such as a sphere. It may have an irregular crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is described in "Chemie et Physique Photographiqu" by P. Glafkides.
e) (published by Paul Montel, 1967), G. F. Duffin
"Photographic Emulsion Chemis"
try) (Focal Press, 1966), V.I. L. Zelikm
an et al, "Manufacturing and Coating of Photographic Emulsions" (Making and Coa
ting Photographic Emulsion) (Focal Press, 19)
64) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A conversion method in which a halogen salt is added so as to form a more sparingly soluble silver halide, and a method of maintaining constant pAg in a liquid phase in which silver halide is produced, as one form of the simultaneous mixing method, That is, the so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rhodan potassium or U.S. Pat. No. 3,271,157;
No. 1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A No. 54-100717, or JP-A No. 54-155828. It can be used in aging and chemical aging.

To remove the soluble silver salt from the emulsion after physical ripening,
Follow Nudell washing, flocculation sedimentation method or ultra-leakage method.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization using thioureas, mercapto compounds, rhodanines); Reduction sensitization using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Metal compounds (eg, gold complex salts, Pt, Ir, Pd, Rh, F
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as e) can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A dye that does not have a spectral sensitizing effect by itself, or a substance that does not substantially absorb visible light, together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (for example, US Pat. Nos. 2,933,390 and 3,6.
35,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,51).
No. 0), cadmium salt, azaindene compound and the like.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance.

In the light-sensitive material of the present invention, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol derivative, etc., as a color antifoggant or a mixing inhibitor. May be included.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 1764
3 (December 1978) and Ibid. 18716 (1979).
, November).

The invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support usually used for photographic light-sensitive materials such as plastic film, paper, cloth or a rigid support such as glass, pottery and metal. To be done.

The support used in the present invention is preferably a baryter paper or a polyethylene-supported paper support containing a white pigment (for example, titanium oxide) in polyethylene.

The silver halide color photographic light-sensitive material of the present invention is suitable for use mainly as a light-sensitive material for direct image observation such as color paper, color reversal paper, color reversal film and color positive film for movies.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N.
-Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- 4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates and the like can be mentioned.

The color developer contains alkali metal carbonate, in addition to preservatives such as alkali metal sulfite and hydroxylamine.
It is common to include a pH buffer such as borate or phosphate; a development inhibitor such as bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. In addition, organic solvents (such as benzyl alcohol and diethylene glycol), polyethylene glycol, quaternary ammonium salts, and development accelerators such as amines may be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds. Typical bleaching agents are ferriciyanides; dichromates; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2.
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates; manganates; nitrosphenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in the stand-alone bleaching solution and the one-bath bleach-fixing solution.

If necessary, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution.

After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the water washing step for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds, magnesium salts and aluminum. A hardening agent typified by a salt, or a surfactant for preventing drying load and unevenness can be added if necessary. Alternatively, L. E. West "Water Quality Criteria", "Science and Engineering of Photography" (Photo.Sci.Eng.), Volume 6, 344
The compounds described on page 359 (1965) and the like may be added. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57 / 57
You may implement the multistage countercurrent stabilization treatment process as described in -8543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 8), Representative examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzoisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenol, etc.), surfactant, fluorescent enhancement Various additives such as whitening agents and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, ammonium chloride as a film pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The silver halide light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.

Typical compounds thereof are JP-A-56-64339,
57-144547, 57-2111147, 58-50532, 58-50536, 58-.
No. 50533, No. 58-50534, No. 58-505.
35 and 58-115438.

The various processing solutions used in the present invention are used at 10 ° C to 50 ° C, but it is preferable to develop at a temperature of 33 ° C to 38 ° C. In addition, West German Patent No. 2, for saving silver in the light-sensitive material
226,770 or US Pat. No. 3,674,499
The treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 1 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Example 1 A sample was prepared by coating the following emulsion layer and protective layer on a cellulose triacetate transparent film support.

To 10.5 g of the coupler M-1 of the present invention, 15 g of tricresyl phosphate and 20 ml of ethyl acetate were added and dissolved by heating at 60 ° C. This solution was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1 g of sodium dodecylbenzenesulfonate. To obtain an emulsified dispersion that was stirred at high speed with a high-speed stirrer. The compositional content of silver chloride and silver bromide was 30 mol% and 70 m based on the total amount of this coupler dispersion.
% of silver chlorobromide with a particle size of 0.45μ
and 150 g of a silver halide emulsion containing 7.5 g of gelatin and gelatin are added and mixed, and 2-hydroxy-4,
A coating solution containing sodium 6-dichloro-s-triazinate was added, and the amount of silver coated on the support was 0.004 mo.
It was applied together with the protective layer so as to be 1 / m ² . This sample was designated as A. Samples prepared by replacing coupler M-1 with couplers M-2 and M-3 in the same manner as in sample A were designated as B and C, respectively. Furthermore, the following comparative coupler X
Samples prepared using -1, X-2, X-3 and X-4, X-5, X-6 in the same manner, substituting equimolar amounts for the coupler M-1, respectively D, E, F and G, H, I
And

Samples A to I were exposed to white light through an optical wedge and then developed by the following processing steps, and sensitometry was performed. The results are shown in Table 1.

In Table 1, the sensitivity is the relative value of the reciprocal of the exposure required to give a density equivalent to fog +1.0, and gamma is the gradation connecting two points corresponding to densities of 1.0 and 1.5. Indicates. The sensitivity was 100 for Sample A.

Samples A, B, and C of the present invention all have a high feeling, a high gradation, and good color development as compared with the other samples. Further, among the samples of the present invention, it can be seen that the sample B is more sensitive than the sample A and the sample C is more sensitive than the sample B.

X-1 X-2 X-3 X-4 X-5 X-6 Treatment process (33 ℃) The components of each processing step are as follows.

Developer Diethylenetriamine pentaacetic acid 1.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Na ₂ SO ₃ 2.0 g KBr 0.5 g Hydroxylamine sulfate 3.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (me- Tansulphonamide) ethyl] -p-phenylenediamine / sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30 g Fluorescent brightener (4,4′-diaminostilbene type) 1.0 g Water was added 1 Make a litter (pH 10.1) Bleach-fixing solution Ammonium thiosulfate (70 wt%) 150 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (EDTA)] 55 g EDTA · 2Na 4 g Add water to make a litter (pH 6.9) Implementation Example 2 30 g of lime-processed gelatin and 5.5 g of sodium chloride
Was dissolved in 1000 cc of distilled water and kept at 55 ° C.
A solution prepared by dissolving 25 g in 1500 cc of distilled water, 600 cc of 8.8 g of potassium bromide and 38.8 g of sodium chloride.
And a liquid dissolved in distilled water in 75 minutes were added and mixed for 75 minutes. This emulsion was desalted and washed with water, and then chemically sensitized with sodium thiosulfate to obtain 1000 g of emulsion a.

Similarly, 30 g of lime-processed gelatin and 5.5 g of sodium chloride were dissolved in 1000 cc of distilled water and kept at 65 ° C.
A solution of 125 g of silver nitrate dissolved in 1500 cc of distilled water, 43.8 g of potassium bromide and 21.6 g of sodium chloride were added to 60 parts.
A solution dissolved in 0 cc of distilled water was added and mixed for 75 minutes. This emulsion was desalted and washed with water, and then chemically sensitized with sodium thiosulfate to obtain 1,000 g of emulsion b.

Similarly, 30 g of lime-processed gelatin and 5.5 g of sodium chloride were dissolved in 1000 cc of distilled water and kept at 75 ° C.
A solution prepared by dissolving 125 g of silver nitrate in 1500 cc of distilled water, 78.8 g of potassium bromide and 4.4 g of sodium chloride was added to 6 parts.
A liquid dissolved in 00 cc of distilled water was added and mixed for 75 minutes. This emulsion was desalted and washed with water, and then chemically sensitized with sodium thiosulfate to obtain 1000 g of emulsion c.

15 g of tricresyl phosphate and 20 ml of ethyl acetate were added to 16.3 g of coupler M-9 of the present invention and dissolved by heating at 60 ° C., and this solution was added to 100 ml of an aqueous solution containing 10 g of gelatin and 1 g of sodium dodecylbenzenesulfonate. The mixture was mixed and stirred with a high-speed stirrer to obtain an emulsified dispersion (a).

Further, as comparative couplers, emulsion dispersions prepared by substituting the following X-7 and X-8 in an equimolar amount with respect to the coupler M-9 were designated as (B) and (C).

X-7 X-8 These emulsified dispersions (a), (b) and (c) were added to the emulsion a,
135 g of each of b and c are combined and mixed, and further sodium 2-hydroxy-4,6-dichloro-s-triazinate is added thereto, and the amount of silver coated is 0.004 mol on the cellulose triacetate transparent film support. It was applied together with the protective layer so as to be / m ² . These samples were designated as J to R.

After exposing the samples J to R to white through an optical wedge,
The same development process as in Example 1 was performed and the results shown in Table 2 were obtained.

The sensitivity and gamma were the same as in Example 1, and the sensitivity was set to 100 for the sample L.

In the comparative couplers X-7 and X-8, the gamma decrease was large in the emulsions a and b having a high silver chloride content, whereas in the coupler M-9 of the present invention, the gamma was not decreased and the silver chloride content was high. It shows a gamma equal to or higher than that of emulsion c having a low rate. It can be seen that the couplers of the present invention tend to exhibit particularly excellent performance for emulsions having a high silver chloride content.

Example 3 A color photosensitive material was prepared by coating a photosensitive layer comprising the following first to seventh layers on a paper support laminated on both sides with polyethylene. The polyethylene coated with the first layer contains titanium dioxide and a trace amount of ultramarine.

(Structure of Photosensitive Layer) The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and the silver halide coating amount indicates the coating amount in terms of silver.

1st layer (blue sensitive layer) Silver chlorobromide emulsion (80 mol% of silver bromide) Silver 0.30 Yellow coupler (* 1) 0.70 Same as above Solvent (TNP) 0.15 Gelatin ………… 1.20 Second layer (intermediate layer) Gelatin ………… 0.90 Di-t-octylhydroquinone ………… 0.05 Same as above Solvent (DBP) …………. 10 Third Layer (Green Sensitive Layer) Silver Chlorobromide Emulsion Emulsion of Example 1 ... Silver 0.22 Magenta Coupler (M-16) ... 0.43 Same as above Solvent (TOP) ... 43 Anti-fading agent (* 2) …… 0.20 Gelatin …… 1.00 Fourth layer (UV absorbing intermediate layer) UV absorber (* 3 / * 4 / * 5) ……… 0 0.06 / 0.25 / 0.25 Same as above Solvent (TNP) ………… 0.20 Gelatin ………… 1.5 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (70 mol% of silver bromide) ...... Silver 0.20 Cyan coupler (* 6 / * 7) ...... 0.2 / 0.2 Coupler solvent (TNP / DBP) ………… … 0.10 / 0.20 Gelatin ………… 0.9 Sixth layer (UV absorbing intermediate layer) UV absorber (* 3 / * 4 / * 5) ………… 0.06 / 0.25 /0.25 Same as above Solvent (DBP) ………… 0.20 Gelatin ………… 1.5 7th layer (protective layer) Gelatin ………… 1.5 Where DBP is dibutyl phthalate and TOP is Tri (n-octyl) phosphate and TNP represent tri (n-nonyl) phosphate.

(* 1) (* 2) (* 3) (* 4) (* 5) (* 6) (* 7) The following dyes were used as the spectral sensitizer for each emulsion layer.

Blue sensitive emulsion layer; (2 × 10 ⁻⁴ mol was added per mol of silver halide.) Green-sensitive emulsion layer; (Addition of 2.5 × 10 ⁻⁴ mol per mol of silver halide.) Red-sensitive emulsion layer; (Addition of 2.5 × 10 ⁻⁴ mol per mol of silver halide.) The following dye was used as an anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; This coated sample was designated as S. A sample prepared by replacing the magenta coupler of the third layer of Sample S with M-16 to M-17 and M-18 in equimolar amounts was used. U Further, the samples prepared by substituting the comparative couplers X-9, X-10, and X-11 were designated as V, W, and X.

Green light was applied to these samples through an optical wedge, and the same developing treatment as in Example 1 was performed to obtain the results shown in Table 3.

The sensitivity and gamma were obtained by the same measurement as in Example 1. The sensitivity was taken as a relative value with the sample S being 100.

The samples S, T, and U of the present invention are all comparative samples V, W, and X.
It can be seen that it shows excellent performance with higher feeling and higher gamma.

Further, among the samples of the present invention, T is superior to S and U is superior to T. A similar tendency shows that the comparative sample V,
Also seen between W and X. However, even if S and X are compared, the comparative sample X does not reach the sample S of the present invention.

X-9 X-10 X-11 Example 4 Fourth on a paper support laminated on both sides with polyethylene
Multi-layer color photographic paper having the layer constitution shown in the table was produced. The coating liquid was prepared as follows.

Preparation of first layer coating solution To 19.1 g of the yellow coupler (a) and 4.4 g of the color image stabilizer (b), 27.2 CC of ethyl acetate and 7.9 CC of the solvent (c) were added and dissolved, and this solution was diluted with 10% dodecyl It was emulsified and dispersed in 185 CC of 10% gelatin aqueous solution containing 8 CC of sodium benzenesulfonate. On the other hand, a blue-sensitive sensitizing dye shown below was added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g / kg of Ag) at 5.0 × 10 ⁻⁴ per mol of silver.
What was added mol was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown in Table 4. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

The following were used as the spectral sensitizing dye for each layer.

Blue-sensitive emulsion layer (5.0 × 10 ⁻⁴ mol per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ⁻⁴ mol per mol of silver halide) and (7.0 × 10 ⁻⁵ mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

4,4'-bis [2,6-di (2-naph-thox
y) pyrimidin-4yl-amino] stilbene-2,2′-di-sulfonic acid Further, for blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer, 1- (5-methylureidophenyl) -5- Mercaptotetrazole is added to 8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol, and 2.5 × 1 mol per mol of silver halide, respectively.
^0-4 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and The structural formulas of the compounds such as the couplers used in this example are as follows.

(A) Yellow coupler (B) Color image stabilizer (C) solvent (D) Mixing inhibitor (E) Magenta coupler (F) Color image stabilizer (G) solvent and 2: 1 mixture (weight ratio) (h) UV absorber and and 1: 5: 3 mixture (molar ratio) of (i) Color mixing inhibitor (J) solvent (K) Cyan coupler (L) Color image stabilizer and and 1: 3: 3 mixture (molar ratio) The obtained color photographic paper sample was exposed through an optical wedge, and then developed in the following processing steps.

Processing time Temperature Color development 45 seconds 35 ° C. Bleach fixing 45 seconds 35 ° C. Rinse 1 minute 30 seconds 30 ° C. (4 tank cascade) Dry 50 seconds 80 ° C. The composition of the processing liquid used is as follows.

Color developer Water 800 CC Diethylenetriaminepentaacetic acid 1.0 g Sodium sulfite 0.2 g N, N-diethylhydroxylamine 4.2 g Potassium bromide 0.01 g Sodium chloride 1.5 g Triethanolamine 8.0 g Potassium carbonate 30 g N-ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5 g 4,4′-diaminostilbene-based fluorescent brightening agent (Sumitomo Chemical Co., Ltd. Whitex 4) 2.0 g Water In addition, with 1000 CC KOH, pH 10.25, bleach-fixing solution water 400 CC ammonium thiosulfate (70%) 150 CC sodium sulfite 18 g ethylenediaminetetraacetic acid (III) ammonium 55
g Ethylenediaminetetraacetic acid 5g Water added 1000CC PH 6.75 Rinse solution 1-Hydroxyethylidene-1,1-disulfonic acid (60%) 1.5CC Nitrilotriacetic acid 1.0g Ethylenediaminetetraacetic acid 0.5g Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.0 g Bismuth chloride (40%) 0.5 g Magnesium sulfate 0.2 g Zinc sulfate 0.3 g Ammonium ban 0.5 g 5-Chloro-2-methyl-4- Isothiazolin-3-one 30 mg 2-Methyl-4-isothiazolin-3-one 10 mg 2-Octyl-4-isothiazolin-3-one 10 mg Ethylene glycol 1.5 g Sulfanilamide 0.1 g 1,2,3-Benzotriazole 1.0 g Ammonium sulfite (40%) 1.0 g Ammonia water ( 6%) 2.6CC Polyvinylpyrrolidone 1.0g 4,4'-diaminostilbene-based brightening agent 1.0g Water was added to 1000CC KOH to give pH 7.0 as a third layer silver chloride emulsion, as shown below. The emulsion prepared in 1. was used.

Add 30 g of lime-processed gelatin to 1000 CC of distilled water,
After melting at 40 ° C, 6.5 g of sodium chloride was added to raise the temperature to 52.5 ° C. A solution prepared by dissolving 62.5 g of silver nitrate in 750 CC of distilled water and 21.5 g of sodium chloride.
Was dissolved in distilled water (500 CC) and the mixture was added to and mixed with the previous solution over 40 minutes while maintaining 52.5 ° C. Further silver nitrate 6
52. A solution of 2.5 g dissolved in 500 CC of distilled water and a solution of 21.5 g of sodium chloride dissolved in 300 CC of distilled water.
The mixture was added and mixed for 20 minutes while maintaining 5 ° C. End of addition 2
After a minute, the sensitizing dye for the green-sensitive emulsion layer was added, and the mixture was left for 15 minutes, washed with demineralized water, and chemically sensitized with 6 × 10 ⁻⁶ mol / Ag / mol sodium thiosulfate.

The coated sample in Table 4 was designated as Y. For sample Y, the magenta coupler (e) of the third layer is illustrated as magenta coupler M-
A coated sample was prepared by substituting 15 in equimolar amounts and designated as sample Z.

The results obtained for samples Y and Z are shown in Table 5.

It is understood that the sample Z using the coupler M-15 of the present invention has higher sensitivity, higher gamma, and is superior to the coupler (e) showing relatively good performance.

Continuation of front page (56) Reference JP-A-59-171956 (JP, A) JP-A-61-120154 (JP, A) JP-A-61-120149 (JP, A) JP-A-62-75530 (JP , A) JP 61-230146 (JP, A) JP 61-230147 (JP, A) European Patent 145342 (EP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion layer containing a pyrazolotriazole coupler represented by the general formula [II]. General formula (II) In the formula, R ₂ , R ₃ and R ₄ each represent a substituted or unsubstituted alkyl group, and R ₆ , R ₇ and R ₈ are each R
_{It has} the same meaning as ₂ , R ₃ and R ₄ , but one of R ₆ , R ₇ and R ₈ may be hydrogen. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.