JPH05150426A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance of a dyestuff image and to prevent discoloration for a long period and to ensure storage stability at high degree by incorporating a specified cyan dyestuff-forming coupler and a nickel complex in at least one layer on a support. CONSTITUTION:The one layer formed on the support contains the cyan dyestuff forming coupler represented by formula I or II and the nickel complex obtained by combing oxygen, sulfur, or nitrogen in the organic compound with it or coordinating it around nickel. In formulae I and II, one of Za and Zb is -N=, and the other is -C(R3)=; each of R1 and R2 is an electron-attractive group having a Hammett's substituent constant sigmap of >=0.20 and the sum of them is >=0.65; R3 is H or a substituent; and X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent. Each of R1-R3 may become a divalent group at X group and combines with the chains of a polymer more than a dimer and polymer to form a homopolymer or copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it uses a pyrrolotriazole-based cyan coupler and a specific Ni complex to improve color developability, color reproducibility and image storability. The present invention relates to an improved silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer which is sensitive to the three primary colors of red, green and blue, and three types of color formers (couplers) in each emulsion layer are provided in respective layers. A color image is reproduced by a so-called subtractive method, in which a color is developed in a relationship between the perceived color and the complementary color. The color image obtained by photographic processing of this silver halide color photographic light-sensitive material is composed of an azomethine dye or an indoaniline dye formed by a reaction between an oxide of an aromatic primary amine color developing agent and a coupler. It is common.

In this silver halide color photographic light-sensitive material, a phenol-type or naphthol-type coupler is generally used for forming a cyan dye image. However, because these couplers have unfavorable absorption in the blue and green regions,
It has a big problem that the color reproducibility is significantly lowered.

As a means for solving this problem, E
2,4-diphenylimidazoles described in P249,453A2 have been proposed. Dyes formed from these couplers have less undesirable absorption on the short-wave side than conventional dyes, which is preferable for color reproduction. However, these couplers cannot be said to have sufficient color reproducibility, their coupling activity is low, and their fastness to heat and light is extremely low. Further, JP-A 64-552 and 64-553.
No. 64, No. 554, No. 64-555, No. 64-5
The pyrazoloazole couplers described in Nos. 56 and 64-557 have improved absorption on the short-wave side as compared with conventional dyes, but have sufficient coloring properties and color reproducibility as a cyan coupler. I can't say.

On the other hand, an ultraviolet absorber, an epoxy compound and a phenylenediamine compound are used for the purpose of improving the fastness of a phenol type, a naphthol type and a dye obtained from a cyan coupler which are generally used as a cyan coupler. -151149, U.S. Pat. No. 4,239,85
No. 1, JP-A-62-178963, and the like, phenol,
Compounds obtained by converting hydroquinone or a phenolic hydroxyl group of catechols into an ether, an ester, a silyl ester, or a phosphoric acid ester are disclosed in JP-A-56-11453 and JP-A-61-1.
No. 679553, No. 64-46751, JP-A-1-28.
4852 and the like include phenols, chromanols, hydroquinones, catechols, and amines.
No. 85547, No. 63-98661, No. 53-775.
No. 27, No. 62-232650, No. 62-21046.
No. 5, JP-A-1-137257, etc., amide compounds,
Polymeric amide compounds are disclosed in European Patent Publication No. 268496,
The metal complex described in JP-A-2-43541 and the like is disclosed in JP-A-62-1
No. 121456, No. 62-121457 and the like.

However, even if these compounds show a sufficient effect on the magenta dye, they are not sufficient on the phenol type, naphthol type and cyan dyes, and even if they show an effect on the light fastness, they are heat fast. If the heat resistance is insufficient or conversely deteriorates, or if the heat resistance is effective, the light resistance is deteriorated.

Further, a pyrazoloazole type cyan coupler,
For the purpose of improving the fastness of the dye obtained from the imidazole type cyan coupler, ultraviolet absorbers proposed for phenol type and naphthol type, hindered phenols, hindered amines, amides, high molecular amides, phosphorus compounds, hydroquinone and catechols are used. Japanese Patent Laid-Open No. 1-149045
Nos. 1-156744, 1-156745, 1-295257, 1-230042, 1-1.
As proposed in Japanese Patent No. 56746, etc., unnecessary secondary absorption on the short wave side was small, but it was insufficient to improve the fastness. On the other hand, a combination of a dye obtained from a pyrroloazole dye-forming coupler and a specific metal complex is disclosed in JP-A-62-162.
No. 291646, No. 62-291651, No. 62-2
No. 91652 is proposed. However, the couplers disclosed in these are those which develop magenta color, and although the effect of improving the fastness is recognized,
It was also insufficient.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in color reproducibility of a dye image, does not discolor for a long period of time and has a high storability. Another object of the present invention is to prevent the color development of the coupler from being adversely affected, to suppress the coloring of the white background, to have a sufficient effect of preventing discoloration or fading of the color image, and to prevent the formation of fine crystals after being applied. Another object of the present invention is to provide a silver halide color photographic light-sensitive material containing an anti-fading agent and having excellent fastness. Another object of the present invention is to provide a silver halide color photographic light-sensitive material which does not discolor a cyan dye image for a long period of time, is particularly excellent in light fastness and has a high storability.
Another object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent color reproducibility, little coloring of a white background even when a dye image is stored for a long period of time, and less loss of balance among the three colors of yellow, magenta and cyan. To provide the material.

[0009]

DISCLOSURE OF THE INVENTION As a result of various investigations, the present inventors have made at least one cyan dye-forming coupler represented by the following general formula (I) or (II) on at least one layer on a support. It has been found that the object of the present invention can be achieved by incorporating at least one nickel complex in which nickel is bonded or coordinated with an oxygen atom, a sulfur atom or a nitrogen atom in an organic compound.

[0010]

[Chemical 2]

In the formula, Za and Zb are each --C (R ₃ ).
Represents = or -N =. However, one of Za and Zb is -N =, the other is -C (R ₃₎ is =. R ₁ and R ₂ each have a Hammett's substituent constant σ _p value of 0.2.
Represents 0 or more electron-withdrawing groups, and σ _{p of} R ₁ and R ₂
The sum of the values is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R ₃ or X may be a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer.

The present invention will be described in detail below. Here, the Hammett's substituent constant σ used in the present specification
_{The p-} value will be explained briefly. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L. et al. P. A rule of thumb put forward by Hammett, which is widely accepted today. There are σ _p values and σ _m values as the substituent constants obtained by the Hammett's rule, and these values can be found in many general textbooks. A. Dean, "Lange '
Handbook of Chemistry ", 12th Edition, 1979 (Mc
Graw-Hill) and "Chemical Area" special edition, No. 122, 96-
Details on page 103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value found in the above-mentioned book. It goes without saying that, even if the value is unknown in the literature, it also includes a substituent that may be included in the range when measured based on Hammett's rule. The compounds represented by the general formulas (I) and (II) of the present invention are not benzene derivatives, but as a measure showing the electron effect of the substituent,
Use the σ _p value regardless of the replacement position. In the present invention, the σ _p value will be used in this meaning from now on.

Unless otherwise specified, the substituent in the present specification may be a substitutable group, for example, an aliphatic group,
Aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, Aliphatic carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino Group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, hydroxy group, cyano group, nitro group, hydroxyamino group, halogen atom and the like.

The cyan coupler of the present invention will be described in detail below. Za and Zb each -C (R ₃₎ = or represent -N =. However, one of Za and Zb is -N =, the other is -C (R ₃₎ is =. That is, the cyan coupler of the present invention is specifically represented by the following general formula (I-
It is represented by a), (Ib), (II-a) and (II-b).

[0015]

[Chemical 3]

(In the formula, R ₁ , R ₂ , R ₃ and X have the same meanings as in formula (I) or (II), respectively.)

R ₃ represents a hydrogen atom or a substituent, and the substituent is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group or an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Examples thereof include phosphonyl group, aryloxycarbonyl group, acyl group and azolyl group. These groups may be further substituted with the substituents exemplified for R ₃ .

More specifically, R ₃ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). , An alkynyl group, a cycloalkyl group, a cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group,
Carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butyl). Phenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {2- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl)) Carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl,
N- (2-dodecyloxyethyl) sulfamoyl, N
-Ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl) , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pi). Valoylaminophenylazo,
2-hydroxy-4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg,
Phenoxycarbonylamino), imide group (eg, N
-Succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-
Benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl) , Phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an azolyl group (for example, imidazolyl, pyrazolyl, 3- Chloro-pyrazol-1-yl, triazolyl).

R ₃ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group. , Sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group, An azolyl group can be mentioned.

More preferably, it is an alkyl group or an aryl group, more preferably an alkyl group or an aryl group having at least one substituent, and more preferably at least one alkoxy group or a sulfonyl group from the viewpoint of aggregation. , An alkyl group or an aryl group having a sulfamoyl group, a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent. When the aryl group has these substituents, it is more preferable that they have at least the ortho position.

In the cyan coupler of the present invention, both R ₁ and R ₂ are electron withdrawing groups of 0.20 or more, and R ₁ is R _1.
When the sum of the σ _p values of R ₂ and R ₂ is 0.65 or more, color is developed as a cyan image. The sum of the σ _p values of R ₁ and R ₂ is preferably 0.70 or more, and the upper limit is about 1.8.

R ₁ and R ₂ are Hammett's substituent constants σ p
It is an electron-withdrawing group having a value of 0.20 or more. Preferably,
It is an electron-withdrawing group of 0.30 or more. The upper limit is 1.
It is an electron-withdrawing group of 0 or less.

Specific examples of R ₁ and R ₂ which are electron withdrawing groups having a σ _p value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, Nitro group, dialkylphosphono group, diarphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, Halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, heterocyclic group , Halogen atom, azo group, or sel An example is a nonocyanate group. The group capable of further having a substituent among these substituents may further have a substituent as described for R ₃ .

[0024] Further details the R ₁ and R _2, σ _p
Examples of the electron withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl). , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, is)
o-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono Group (for example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenylsulfinyl) ,
Alkylsulfonyl group (for example, methanesulfonyl, octanesulfonyl), arylsulfonyl group (for example,
Benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio,
Benzoylthio), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a thiocyanate group, a thiocarbonyl group (for example, methylthiocarbonyl, phenylthiocarbonyl), a halogenated alkyl group (for example,
Trifluoromethane, heptafluoropropane), halogenated alkoxy groups (eg trifluoromethyloxy), halogenated aryloxy groups (eg pentafluorophenyloxy), halogenated alkylamino groups (eg,
N, N-di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,
1,2,2-tetrafluoroethylthio), σ _p 0.20
An aryl group substituted with another electron-withdrawing group (for example, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-benzoxazolyl, 2-benzothiazolyl,
1-phenyl-2-benzimidazolyl, 5-chloro-
1-tetrazolyl, 1-pyrrolyl), a halogen atom (eg chlorine atom, bromine atom), an azo group (eg phenylazo) or a selenocyanate group. Among these substituents, a group which can further have a substituent is R ₃
It may further have a substituent such as those mentioned above.

Preferred as R ₁ and R ₂ are an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, Arylsulfonyl group, sulfamoyl group, halogenated alkyl group,
Halogenated alkyloxy group, halogenated alkylthio group, halogenated aryloxy group, two or more σ _p 0.
An aryl group substituted with 20 or more other electron-withdrawing groups,
And heterocyclic groups. More preferably,
An alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. Most preferred as R ₁ is a cyano group. Particularly preferred as R ₂ is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group.

X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. The splittable group is specifically described as a halogen atom, an alkoxy group or an aryloxy group. Group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5 member or 6 Membered nitrogen-containing heterocyclic group, imide group, arylazo group, etc., and these groups may be further substituted with a group acceptable as a substituent for R ₃ .

More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dothesyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryloxy. A group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,
1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X may contain a photographically useful group such as a development inhibitor or a development accelerator.

Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, and a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. More preferable X
Is a halogen atom, an alkyl or arylthio group, and particularly preferably an arylthio group.

In the cyan coupler represented by the general formula (I) or (II), the group of R ₁ , R ₂ , R ₃ or X becomes a divalent group, and a dimer or higher polymer or polymer. It may combine with a chain to form a homopolymer or a copolymer. The homopolymer or copolymer bound to the polymer chain means an addition polymer having a cyan coupler residue represented by the general formula (I) or (II), a homopolymer or copolymer of an ethylenically unsaturated compound. This is a typical example. In this case, one or more kinds of cyan color-forming repeating units having a cyan coupler residue represented by the general formula (I) or (II) may be contained in the polymer, and a non-color-forming ethylene as a copolymer component. It may be a copolymer containing one type or two or more types of type monomers. The cyan color-forming repeating unit having a cyan coupler residue represented by the general formula (I) or (II) is preferably represented by the following general formula (P).

[0030]

[Chemical 4]

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -C.
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO 2 -
Or it represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom is removed from R ₁ , R ₂ , R ₃ or X of the compound represented by the general formula (I) or (II). As the polymer, a copolymer of a cyan color-forming monomer represented by the coupler unit of the general formula (I) or (II) and a non-color-forming ethylene-like monomer which is not coupled with an oxidation product of an aromatic primary amine developing agent is preferable.

As the non-color-forming ethylene type monomer which is not coupled with the oxidation product of the aromatic primary amine developing agent,
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) An amide or ester derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, dimethacrylate). Acetone acrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg vinyl acetate, vinyl propio). And vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene),
Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid ester, N-vinyl-2-
Pyrrolidone, N-vinyl pyridine and 2- and -4
-Such as vinyl pyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above general formula (I) or (II) is the physical property of the copolymer to be formed. Properties and / or chemical properties, such as solubility, compatibility of the photographic colloid composition with binders such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced.

In order to incorporate the cyan coupler of the present invention into the silver halide light-sensitive material, preferably in the red light-sensitive silver halide emulsion layer, it is preferable to use a so-called internal type coupler, and for that purpose, R ₁ and R _At least one of ₂ , R ₃ and X is a so-called ballast group (preferably having a total carbon number of 1).
It is preferably 0 or more), and more preferably 10 to 50 carbon atoms in total. It is particularly preferable that R ₃ has a ballast group. In the present invention, the general formula (I)
The cyan coupler represented by the formula (1) is preferable in terms of effect, and the cyan coupler represented by the general formula (Ia) is particularly preferable in terms of effect. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

Next, a synthesis example of the cyan coupler of the present invention will be shown and the synthesis method will be described. Synthesis Example 1 (Synthesis of Exemplified Compound (1))

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

3-m-nitrophenyl-5-methylcyano-1,2,4-triazole (1) (20.0 g, 8
7.3 mmol) was dissolved in 150 ml of dimethylacetamide, and NaH (60% in oil) (7.3 g) was added little by little to it.
183 mmol) was added and heated to 80 ° C. Add 50 ml of ethyl bromopyruvate (13.1 ml, 105 mmol) to this.
The ml dimethylacetamide solution was slowly added dropwise. After dropping, the mixture was stirred at 80 ° C. for 30 minutes and cooled to room temperature. The reaction solution was acidified by adding 1N hydrochloric acid, extracted with ethyl acetate, dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 10.79 g (38%) of compound (2).

Reduced iron (9.26 g, 166 mmol) and ammonium chloride (0.89 g, 16.6 mmol) were suspended in 300 ml of isopropanol, and further 30 ml of water and 2 ml of concentrated hydrochloric acid were added.
ml was added, and the mixture was heated under reflux for 30 points. While heating under reflux
Compound (2) (10.79 g, 33.2 mmol) was added in small portions. After heating under reflux for 4 hours, the mixture was immediately filtered through Celite, and the filtrate was evaporated under reduced pressure. The residue was dissolved in a mixed solution of 40 ml of dimethylacetamide and 60 ml of ethyl acetate, compound (3) (25.6 g, 36.5 mmol) was added, and then triethylamine (23.1 ml, 166 mmol) was added, and the mixture was heated at 70 ° C. at 5 ° C. Heat for hours. The reaction solution was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with water and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to give compound (4) 1
6.5 g (52%) could be obtained.

Compound (4) (7.0 g, 7.30 mmol) was dissolved in 14 ml of isobutanol, tetraisopropyl orthotitanate (0.43 ml, 1.46 mmol) was added, and
Heated to reflux for hours. The reaction solution was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. After drying with sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 5.0 g (69%) of compound (5).

Compound (5) (5.0 g, 5.04 mmol) was dissolved in 50 ml of tetrahydrofuran and SO ₂ Cl ₂ was added under water cooling.
(0.40 ml, 5.04 mmol) was added dropwise, and after the addition, the mixture was stirred under water cooling for 4 hours. Water was added to the reaction solution, which was extracted with ethyl acetate, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 3.9 g (76%) of Exemplified compound (1).

Synthesis Example 2 (Exemplified Compound (39))

[0061]

[Chemical formula 24]

36% of 2-amino-5-chloro-3,4-dicyanopyrrole (6) (6.78 g, 40.7 mmol)
38 ml of hydrochloric acid was added, and sodium nitrite (2.
A solution of 95 g, 42.7 mmol) in water (5.9 ml) was slowly added dropwise, and stirring was continued for 1.5 hours to synthesize a compound (7). To a solution prepared by adding 102 ml of 28% sodium methylate to a solution of compound (8) (9.58 g, 427 mmol) in 177 ml of ethanol under stirring with ice cooling, slowly add the solution of compound (7) synthesized above under stirring with ice cooling. Was added dropwise, and then stirring was continued for 1 hour. Then, the reaction solution was heated under reflux with stirring for 1.5 hours. Then, ethanol was distilled off from the reaction solution under reduced pressure, the residue was dissolved in chloroform, washed with saturated saline, dried over sodium sulfate, and then chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 4.19 g of compound (10) (2% from yield (6)).
9%).

The compound (6) was synthesized by chlorinating the 3,4-dicyanopyrrole, followed by nitration and iron reduction. In addition, the compound (8) was synthesized by a known method from γ-lactone and benzene.
From the “Journal of the American Chemical Society”
ciety), 76, 3209 (1954).

[0064]

[Chemical 25]

Powdered reduced iron (3.3 g, 59.0 mmol)
Water 10 ml, ammonium chloride (0.3 g, 5.9 mmo
l) and acetic acid (0.34 ml, 5.9 mmol) were added and 1
After heating and refluxing stirring for 5 minutes, 31 ml of isopropanol was added, and the mixture was further heated and refluxed for 20 minutes with stirring. Next, (10) (4.
1 g, 11.8 mmol) in 14 ml of isopropanol was added dropwise, the mixture was heated under reflux with stirring for 2 hours, the reaction mixture was filtered using Celite as a filter aid, and the residue was washed with ethyl acetate.
The solution was evaporated under reduced pressure.

The residue was dissolved in a mixed solution of 16 ml of ethyl acetate and 24 ml of dimethylacetamide, and (11) (5.6 g,
13.0 mmol) was added, and triethylamine (8.2
ml, 59.0 mmol) was added, and the mixture was stirred at room temperature for 4 hours.
Water was added, the mixture was extracted with ethyl acetate, and the extract was washed with saturated saline. After drying with sodium sulfate, the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography, and the exemplified compound (39)
Could be obtained 6.46 g (76%).

Next, the nickel complex of the present invention will be described. The nickel complex described in the present invention is a compound in which nickel is bonded or coordinated with an oxygen atom, a sulfur atom or a nitrogen atom in an organic compound, and preferably the following general formulas (AI) to (A to IV). ) Is a compound represented by.

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

In the general formulas (A-I) and (A-II), R _{a1 to} R _a6 may be the same or different and each represents a hydrogen atom, an alkyl group (eg methyl, ethyl, t-butyl, benzyl, undecyl). , Cyclohexyl), an alkenyl group (eg, vinyl, allyl), or aryl (eg, phenyl, 4-dodecyloxyphenyl), which are adjacent to each other among R _{a1 to} R _a3 and R _{a4 to} R _a6. The groups may combine to form a 5- to 8-membered ring (for example, a benzene ring, a cyclohexene ring, a pyrazole ring). X _a1 and X _a3 may be the same or different, and O, S
Or N (R _a31 ), X _a2 is O, S or N (R
_a32 ). Here, R _a31 is an alkyl group (eg, methyl, ethyl, octyl, cyclohexyl, benzyl), an aryl group (eg, phenyl, 4-methoxyphenyl), an acyl group (eg, acetyl, benzoyl), a hydroxy group, or a sulfonyl group. (Eg, methanesulfonyl, benzenesulfonyl, octanesulfonyl), R _a32 represents a hydrogen atom, an alkyl group (eg, methyl, ethyl, propyl, dodecyl, benzyl,
Cyclohexyl, methoxyethyl), aryl groups (eg phenyl, 4-methoxyphenyl, 4-chlorophenyl), hydroxyl groups, alkoxy groups (eg methoxy, ethoxy, cyclohexyloxy, benzyloxy), aryloxy groups (eg phenoxy, 4-t
-Octylphenoxy, 4-methoxyphenoxy) or a substituted amino group (e.g. dimethylamino,
Octylamino, anilino, N-methyl-N-phenylamino, dioctylamino, acetylamino, methanesulfonamide, benzenesulfonamide). Z
₁ represents an alkylene group (eg ethylene, propylene). When X _{a1 in the} general formula (AI) is N (R _a31 ),
Two R _a31 may be bonded.

In the general formulas (A-III) and (A-IV), R _{a11 to} R _a14 and R _{a18 to} R _a25 may be the same or different and each represents a hydrogen atom, an alkyl group (eg, methyl, ethyl, Octyl, t-butyl, cyclohexyl, benzyl), alkenyl groups (eg allyl,
Vinyl) or an aryl group (eg, phenyl, 4-methoxyphenyl), R _a11 and R _a12 , R _a13 and R _a14 , R _a18 and R _a19 , R _a20 and R _a21 , R _a22 and R _a22.
a23 and R _a24 and R _a25 may combine with each other to form a 5- to 8-membered ring (for example, a benzene ring or a cyclohexene ring). R _{a15 to} R _a17 may be the same or different and each is a hydrogen atom, an alkyl group (eg, methyl, ethyl, octyl, benzyl, cyclohexyl), an alkenyl group (eg, allyl, vinyl) or an aryl group (eg, phenyl, 4 _{-Dodecyloxyphenyl} ) and R _a15
Two or three of R _a17 are bound to each other,
A 5- to 8-membered nitrogen-containing heterocycle (eg, piperidine ring, morpholine ring) may be formed. X _a4 , X _a6 , X _a7 and X _a12 represent O, S or N (R _a33 ), and X _a5 , X
_a8 and X _a11 represent O or S. X _a9 and X
_a10 is a hydroxy group, a mercapto group or N (R _a33 ) (R
_a33 '). Here, R _a33 and R _a33 ′ are a hydrogen atom, an alkyl group (eg, methyl, ethyl, benzyl, cyclohexyl, octyl), an aryl group (eg, phenyl,
4-methoxyphenyl) or a hydroxy group.

In the general formula (AI) of the present invention, preferred compounds in view of the effects of the present invention are listed. A compound in which R _a1 and R _a2 are bonded to each other to form a benzene ring which may have a substituent. _-A compound in which X _a1 is O. A compound in which X _a2 is N (R _a32 ). (More preferable when _Xa2 is N-OH.)-A compound in which _Ra3 is a hydrogen atom or an alkyl group. (R
More preferably, _a3 is a hydrogen atom. ) A compound represented by the general formula (AI) in which the total number of carbon atoms is 20 or more.

In the general formula (A-II) of the present invention, preferred compounds are listed from the viewpoint of the effects of the present invention. A compound in which R _a1 and R _a2 and R _a4 and R _a5 are bonded to each other to form a benzene ring which may have a substituent. A compound in which both X _a1 and X _a3 are O. A compound in which R _a3 and R _a6 are a hydrogen atom or an alkyl group. (It is more preferable when these are hydrogen atoms.) A compound in which Z ₁ is an ethylene group. -The total carbon number of the compound represented by formula (A-II) is 2
A compound which is 0 or more.

In the general formula (A-III) of the present invention, preferable compounds in view of the effects of the present invention are listed. A compound in which R _a11 and R _a12 and R _a13 and R _a14 are bonded to each other to form a benzene ring which may have a substituent. A compound in which X _a4 and X _a6 are O or S. (The most preferable when these are O.) The compound whose X _a5 is S. A compound in which one of R _a15 , R _a16 and R _a17 is a hydrogen atom. -The total carbon number of the compound represented by formula (A-III) is 2
A compound which is 0 or more. (A compound having a total carbon number of 30 or more is more preferable.)

In the general formula (A-IV), preferable compounds in view of the effects of the present invention are listed. A _compound in which R _a18 and R _a19 , R _a20 and R _a21 , R _a22 and R _a23, and R _a24 and R _a25 are bonded to each other to form a benzene ring which may have a substituent. A compound in which X _a7 and X _a12 are O or S. (More preferred when these are O.) Compounds in which X _a9 and X _a10 are hydroxyl groups. A compound in which X _a8 and X _a11 are S. -The total number of carbon atoms of the compound represented by formula (A-IV) is 3
A compound which is 0 or more.

Among the compounds represented by the general formulas (AI) to (A-IV) of the present invention, the compounds represented by the general formulas (AI) and (A-II) in view of the effects of the present invention. Are preferred, and the compounds represented by formula (AI) are most preferred. Specific examples of the Ni complex of the present invention are shown below, but the present invention is not limited thereto.

[0077]

[Chemical 28]

[0078]

[Chemical 29]

[0079]

[Chemical 30]

[0080]

[Chemical 31]

[0081]

[Chemical 32]

[0082]

[Chemical 33]

[0083]

[Chemical 34]

[0084]

[Chemical 35]

[0085]

[Chemical 36]

[0086]

[Chemical 37]

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

The nickel complex of the present invention is described in JP-B-62-2.
8182, JP-A-63-47765, 63-47.
No. 763, No. 62-270666, No. 62-2706.
No. 65, No. 62-175741, No. 59-13239.
No. 63-153544, No. 62-127841
No. 63-47764, Japanese Patent Publication No. 61-13741
No. 62-67536, 61-140941.
No. 62, No. 62-232642, No. 63-47762,
Japanese Patent Publications No. 62-232642, No. 61-13740,
61-13739, JP-A-63-47762, 63-199248, JP-B-61-13744, 61-13741, 61-13742, and JP-A-6.
2-69266, 63-98660, 63-1
53545, 62-169153, 62-13.
No. 1257, No. 64-75491, No. 64-7427
No. 2, 64-73347, JP-A-1-267535.
No. 1-267534, and JP-A No. 1-1606.
Specific compound examples described in the specification such as No. 83 are also preferable,
As the synthetic method, the method described in these specifications or a method similar thereto can be used, but there are also commercially available compounds, which are easily available.

The Ni complex of the present invention varies depending on the type of coupler, but is 0.5 with respect to 1 mol of the coupler used.
The range is ˜200 mol%, preferably 1 to 100 mol%, and most preferably 1 to 50 mol%. The Ni complex of the present invention has the general formula (I) or (II) in view of the effects of the present invention.
It is particularly preferable when it is used by being co-emulsified with the coupler represented by.

The Ni complex of the present invention may be used in combination with a known anti-fading agent, in which case the anti-fading effect is further enhanced. Similarly, two or more Ni complexes may be used together. From the viewpoint of the effect of the present invention, the silver halide color photographic light-sensitive material containing the pyrrolotriazole-based cyan dye-forming coupler of the present invention and the nickel complex of the present invention is used in combination with a pyrazolotriazole-based magenta dye-forming coupler. Is preferred.

The light-sensitive material of the present invention may have at least one layer containing the cyan coupler of the present invention and the Ni complex of the present invention on the support, and the layer may be a hydrophilic colloid on the support. It may be a layer. Common photosensitive materials are
A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer can be formed by coating at least one layer in this order on a support.
The order may be different from this. Also, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is carried out by containing a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the coloring hue of the color coupler may not have the above correspondence. When the cyan coupler of the present invention and the Ni complex of the present invention are applied to a light-sensitive material, they are preferably used in a red-sensitive silver halide emulsion layer. The content of the cyan coupler of the present invention in the light-sensitive material is appropriately 1 × 10 ⁻³ to 1 mol, preferably 2 mol, per mol of silver halide.
It is from x10 ^-3 mol to 3x10 ^-1 mol.

Cyan coupler of the present invention and Ni of the present invention
The complex can be introduced into the light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (a low-boiling organic solvent is optionally used together), and is emulsified and dispersed in a gelatin aqueous solution to be added to a silver halide emulsion. The oil droplet dispersion method is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat.
No. 322,027. In addition, the steps and effects of the latex dispersion method as one of the polymer dispersion methods, and specific examples of the latex for impregnation are described in US Pat.
99,363, West German Patent Application No. (OLS) 2,54
No. 1,274, No. 2,541,230, Japanese Patent Publication No. 53-
No. 41091 and European Patent Publication No. 029104, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

As the high-boiling-point organic solvent that can be used in the above-mentioned oil-in-water dispersion method, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2 , 4-di-tert-
Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphones (for example, diphenylphosphate, triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, dioctylbutylphosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (for example, 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-). p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllaurylamide), alcohols Or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, Tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivative (N, N-dibutyl-)
2-butoxy-5-tert-octylaniline, etc., chlorinated paraffins (paraffins having a chlorine content of 10% to 80%) trimesic acid esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (For example, 2,4-di-tert-
Amylphenol, 4-dodecyloxyphenol, 4
-Dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (For example, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid), etc. Further, as an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and about 160 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.The high boiling point organic solvent is used in an amount of 0 to 2.0 times, preferably 0 to 1.0 times the weight ratio of the coupler. Can be used.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied to process the light-sensitive material. As the agent, those described in the following patent publications, particularly European Patent EP0,355,660A2 are preferably used.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

[0103]

[Table 4]

[0104]

[Table 5]

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a silver chlorobromide or pure silver chloride emulsion having a silver chloride content of substantially 90 mol% or more, further 95% or more, and particularly 98% or more, which does not substantially contain silver iodide.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image or the like, and the hydrophilic colloid layer is described in EP No. 0,337,490A2.
A dye decolorizable by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetravalent alcohol (eg, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole-based magenta coupler.

That is, the compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. Are preferable, for example, in order to prevent stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage after processing.

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

As a support used in the light-sensitive material of the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726. As a result, the light color mixture is removed, and the color reproducibility is significantly improved.

The present invention can be applied to, for example, color papers, color reversal papers, direct positive color photosensitive materials, color negative films, color positive films, color reversal films and the like. Of these, application to a color light-sensitive material having a reflective support (eg, color paper, color reversal paper) or a color light-sensitive material for forming a positive image (eg, direct positive color light-sensitive material, color positive film, color reversal film) is preferable, and particularly It is preferably applied to a color light-sensitive material having a reflective support.

In the practice of the present invention, it is used in combination with a magenta dye-forming coupler and a yellow dye-forming coupler capable of forming magenta and yellow by coupling with an oxidation product of an aromatic primary amine color developing agent. Preferably. In some cases, it is also preferable to use it in combination with a conventionally known phenol type or naphthol type cyan dye forming coupler.

The couplers used in combination with these may be 4 equivalents or 2 equivalents with respect to silver ion, and may be in the form of polymer or oligomer. Further, the couplers to be used in combination may be a single type or a mixture of two or more types.

The couplers preferably used in the present invention in combination with the cyan coupler of the present invention are described below. Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat. No. 4,052,212,
No. 4,146,396, No. 4,228,233
No. 4,296,200, No. 2,369,92
No. 9, No. 2,801,171, No. 2,772,1
No. 62, No. 2,895,826, No. 3,772,
No. 002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication 3,329,729, European Patent 121,365.
A, No. 249,453A, US Pat. No. 3,44
No. 6,622, No. 4,333,999, No. 4,7
75,616, 4,451,559, 4,
Those described in, for example, 427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Further, JP-A 64-553, 64-554 and 6
The pyrazoloazole couplers described in 4-555 and 64-556 and the imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used in combination.
A particularly preferable cyan coupler is JP-A-2-13.
The couplers of general formulas (C-I) and (C-II) described on page 17, lower left column to page 20, lower left column of No. 9544 are mentioned.
These cyan couplers may be used in the same layer as the cyan coupler of the present invention or in a different layer as long as the effects of the present invention are exhibited.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 04795 are more preferable. Particularly preferred magenta couplers are disclosed in JP-A-2-139544, page 3, lower right column to page 10, lower right column, pyrazoloazole-based magenta couplers of general formula (I) and JP-A-2-139544. Page 17, bottom left column
An example is the 5-pyrazolo magenta coupler of the general formula (MI) in the upper left column of page 21. Most preferred are the above-mentioned pyrazoloazole-based magenta couplers.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
European Patent No. 249,473A, JP-A-63-2314
5, 63-123047, and JP-A-1-25094.
No. 4, No. 1-213648 and the like can be used in combination unless the effects of the present invention are impaired. A particularly preferable yellow coupler is a yellow coupler represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, European Patent Publication No. 04479.
No. 69, an acylacetamide-based yellow coupler characterized by an acyl group, and EP-A-0446863.
A yellow coupler of the general formula (Cp-2) described in A2 is mentioned.

Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers that release development inhibitors are described in RD magazine No. 1
7643, Patents described in VII to F, JP-A-57-
151944, 57-154234, 60-1
84248, 63-37346, and U.S. Pat. No. 4,2.
Those described in 48,962 and 4,782,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59-
Those described in 157638 and 59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. No. 4,283,472.
No. 4,338,393, 4,310,618, and the like, multi-equivalent couplers, JP-A-60-185950.
No. 62-242252 and the like, DIR redox compound releasing coupler, DIR coupler releasing coupler, D
IR coupler-releasing redox compound or DIR redox-releasing redox compound, EP 173,30
No. 2A, a coupler that releases a dye that recolors after withdrawal, No. RD magazine. 11449, No. No. 24241,
Bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, etc., and leuco dye-releasing couplers described in JP-A-63-75747. U.S. Pat. No. 4,7
Examples thereof include couplers releasing a fluorescent dye described in JP-A No. 74,181.

The standard amount of these color couplers which can be used in combination in the present invention is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0 in the yellow coupler. 0.01 to 0.5 mol, 0.003 to 0.3 mol for magenta couplers, and 0.002 to 0.3 mol for cyan couplers.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative,
It may contain a gallic acid derivative, an ascorbic acid derivative or the like.

In order to prevent the cyan dye image from being deteriorated by heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer. As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), a 4-thiazolidone compound (for example, US Pat. Nos. 3,314,794 and 3) , 352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
705,805 and 3,707,395), butadiene compounds (US Pat. No. 4,045,22).
9) or a benzoxazole compound (for example, US Pat. Nos. 3,406,070 and 4,27).
Those described in No. 1,307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted in a specific layer. Among them, the benzotriazole compound substituted with the above aryl group is preferable.

The light-sensitive material according to the present invention has the above-mentioned RDN.
o. 17643, pages 28-29, and ibid. 18716
615 can be developed by the usual method described in the left column to the right column. For example, a color development processing step,
A desilvering process and a water washing process are performed. In the desilvering step, instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing processing step using a bleach-fixing solution can be performed, a bleaching processing step, a fixing processing step, The bleach-fixing steps may be combined in any order. The stabilizing step may be performed instead of the washing step, or the stabilizing step may be performed after the washing step. Color development,
A monobath processing step using a one-bath development bleach-fix processing solution in which bleaching and fixing are carried out in one bath can also be carried out. In combination with these processing steps, a pre-hardening step, a neutralizing step thereof, a stop-fixing step, a post-hardening step, an adjusting step, an intensifying step and the like may be performed. An intermediate water washing step may be optionally provided between the above steps. In these processes, a so-called activator processing step may be performed instead of the color development processing step.

[0125]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to give A multilayer color photographic paper (101) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of First Layer Coating Solution Yellow coupler (ExY) 136.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 23 g, solvent (Solv-2) 23
g, and 180 cc of ethyl acetate and dissolved in 10
% Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A of 0.70 μm)
Mixture (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and silver bromide of 0.3 mol% was locally contained in a part of the grain surface in each size emulsion). In this emulsion, the blue-sensitive sensitizing dyes A and B shown below were respectively added to large-sized milk A per mol of silver of 2.0.
To the emulsion of × 10 ^-4 and the small size emulsion A, 2.5 × 10 ^-4 mol was added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.
The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

Preparation of coating liquid for fifth layer Cyan coupler (ExC) 30.0 g, ultraviolet absorber (UV-2) 18.0 g, color image stabilizer (Cpd-1) 2
5.0 g, color image stabilizer (Cpd-9) 15.0 g, color image stabilizer (Cpd-10) 15.0 g, color image stabilizer (Cp
d-11) 1.0 g, color image stabilizer (Cpd-8) 1.0
g, color image stabilizer (Cpd-6) 1.0 g, solvent (Sol
v-6) 25.0 g and solvent (Solv-1) 1.0 g were dissolved by adding 60.0 cc of ethyl acetate, and this solution was added to 500 cc of 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, An emulsified dispersion C was prepared by emulsifying and dispersing with an ultrasonic homogenizer. On the other hand, silver chlorobromide emulsion C (cube, average grain size 0.50
A 1: 4 mixture of a large size emulsion C having a size of μm and a small size emulsion C having a size of 0.41 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was adjusted to 0.09 and 0.11, respectively, and for each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface). In this emulsion, the red sensitizing dye E shown below is 0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻ for small size emulsion C per mol of silver. ⁴ mol is added. Further, compound F shown below was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion C and this red-sensitive silver chlorobromide emulsion C were mixed and dissolved, and a fifth layer coating solution was prepared so as to have the composition shown below.

Coating solutions for the second to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, the total amount of Cpd-14 and Cpd-15 is 25.
The amount added was 0 mg / m ² and 50 mg / m ² . The spectral sensitizing dyes used in the silver chlorobromide emulsion of each photosensitive emulsion layer are shown below.

[0130]

[Table 6]

[0131]

[Table 7]

[0132]

[Table 8]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion agent layer and the red-sensitive emulsion layer at 8.5 × 10 5 per mol of silver halide. ^-5 mol, 7.7 x 10 ^-4
Mol, 2.5 × 10 ⁻⁴ mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ⁻⁴ mol was added. In addition, the following dyes (the coating amount remains in parentheses) were added to the emulsion layer to prevent irradiation.

[0134]

[Chemical 44]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0136]

[Table 9]

[0137]

[Table 10]

[0138]

[Table 11]

[0139]

[Table 12]

[0140]

[Chemical 45]

[0141]

[Chemical 46]

[0142]

[Chemical 47]

[0143]

[Chemical 48]

[0144]

[Chemical 49]

[0145]

[Chemical 50]

[0146]

[Chemical 51]

[0147]

[Chemical 52]

[0148]

[Chemical 53]

First, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of a light source of 3200 °) was used as sample 101
K) was used to give a gray exposure such that about 30% of the coated silver amount was developed. The exposed sample was subjected to continuous processing by using a paper processor with the following processing steps and a solution having a processing solution composition to prepare a developing processing state in a running equilibrium state.

[0150]

[Table 13]

The composition of each processing solution is as follows.

[0152]

[Table 14]

[0153]

[Table 15]

Next, the fifth layer coupler (Ex
C) is replaced by an equimolar amount to the coupler of the present invention, and 25% by weight of the anti-fading agent shown in Tables 16 to 18 relative to the coupler, and the anti-fading agent shown in Table 19 relative to the coupler. Samples were prepared in the same manner except that 5, 10, 30, 50, and 100% by weight were added. The structures of couplers used as comparative compounds in the present invention are shown below.

[0155]

[Chemical 54]

These samples were subjected to three-color separation exposure and then treated with the above running treatment liquid, and the density was measured with red light. Next, these samples were irradiated with xenon light (5 hours light /
After bleaching for 7 days by intermittent irradiation for 1 hour in dark), the density was measured again with red light to determine the residual ratio (%) of the color image at the point where the initial density was 1.5. The results are shown in Tables 16 to 19.

[0157]

[Table 16]

[0158]

[Table 17]

[0159]

[Table 18]

[0160]

[Table 19]

In the table, the maximum color density (Dmax) immediately after processing is shown.
I also showed it. It was visually observed that all the couplers of the present invention had a clear and clean cyan color as compared to the comparative coupler R-1. In addition, No. in the table 24
28 to 28 show the measurement results of the known pyrrolotriazole type magenta coupler M-1. For this coupler, the magenta coupler (ExM) of the third layer of Sample 101 is used.
A sample was prepared in the same manner as the sample 101 except that the equimolar substitution was performed, and the optical density was measured using green light.

As is clear from the table, the known comparative compounds R-2 and R-3, which have excellent hues, show extremely poor fading. When the anti-fading agent of the present invention was used in combination, although a slight improvement was observed, it could not be said to have reached a level that is practically satisfactory.

Further, the known pyrrolotriazole type magenta coupler M-1 is still poor in color fading, and even in this case, the use of the anti-fading agent of the present invention causes little improvement.

On the other hand, it can be said that the pyrrolotriazole type cyan coupler of the present invention is remarkably effective in practical use in combination with the anti-fading agent of the present invention.

Example 2 The present invention shown in Example 1 of the present application for EX-2 of the third, fourth and fifth layers of the multilayer color light-sensitive material sample 101 of Example 1 of JP-A-3-213853. Was replaced with the cyan coupler of Example 1, and 20% by weight of the anti-fading agent of the present invention shown in Example 1 of the present application was added to the coupler to prepare a sample.
Process No. 1 of Example 1 of JP-A-3-213853. 1-6
I did it in. Also for this sample, the method according to Example 1 of the present application (photobleaching: under a fluorescent lamp for 7 days, dark fading 60 ° C.-7)
The fading was evaluated under 0% RH for 1 month).
In this case as well, almost the same results as in Example 1 of the present application were obtained. Furthermore, ExY-1 and ExY-2 are respectively the following Ex
The same evaluation was performed on the samples prepared by substituting Y-3 and ExY-4 so as to be equimolar. In this case, almost the same result was obtained.

[0166]

[Chemical 55]

Example 3 Third layer of Sample 101 of Example 1 of JP-A-2-854,
Cyan couplers C-1, C-2, C- of the fourth and fifth layers
6 and C-8 were replaced by equimolar amounts in the cyan coupler of the present invention shown in Example 2 of the present application, and 25% by weight of the anti-fading agent shown in Example 1 of the present application was added to the coupler. A sample was prepared and described in JP-A-2-854 Example 1
The treatment described in 1. was performed. Also for this sample, Example 1
Evaluation of fading was carried out in the same manner as in. In this case as well, almost the same results as in Example 1 were obtained.

Example 4 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, ExC-1 of the third and fourth layers was used.
Alternatively, ExC-2 is used as the coupler (1) of the present invention,
(2), (15), (16), (19), (20), or (39) is replaced with an equimolar amount, and the nickel complex of the present invention, N-1, N is further used for the third layer and the fourth layer. -6, N-
8, N-10, N-9, N-24, N-32, N-3
A sample was prepared in the same manner as in the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, except that 4, N-38 or N-39 was added in an amount of 20% by weight to the coupler. In addition, in these samples, the magenta coupler ExM1 or ExM2 of the sixth layer or the seventh layer is used.
Is replaced with ExM-3 in an equimolar amount, and the eleventh layer or the twelfth layer is
A sample was prepared in the same manner as the above sample except that the yellow coupler ExY-1 in the layer was replaced with ExY-2 in an equimolar amount.

[0169]

[Chemical 56]

These samples were exposed and developed in the same manner as in Example 1 described in JP-A-1-158431, and the fading test and photographic characteristics were examined. The samples of the present invention showed excellent anti-fading effect. The photographic properties and hue were also good. It has been found that the compound of the present invention exhibits excellent effects even in this light-sensitive material system.

[0171]

The silver halide photographic light-sensitive material in which the pyrrolotriazole cyan coupler represented by the general formula (I) or (II) of the present invention and the nickel complex of the present invention are combined exhibits excellent image fastness, The photographic characteristics and hue were also good.

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[Procedure amendment]

[Submission date] May 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1] (In formula, Za and Zb are -C (R < ₃ >) = or-, respectively.
Represents N =. However, one of Za and Zb is -N.
= And the other is -C (R ₃ ) =. R ₁ and R ₂
Each represents an electron-withdrawing group having a Hammett's substituent constant σ _P value of 0.20 or more, and the sum of σ _P values of R ₁ and R ₂ is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R ₃ or X may be a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. )

[Procedure Amendment 2]

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[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in color reproducibility of a dye image, does not discolor for a long period of time and has a high storability. Another object of the present invention is to prevent the color development of the coupler from being adversely affected, to suppress the coloring of the white background with the passage of time, to have a sufficient effect of preventing discoloration and fading of the color image, and to form fine crystals after being applied. An object of the present invention is to provide a silver halide color photographic light-sensitive material containing an anti-fading agent that does not exist and having excellent fastness. Another object of the present invention is to provide a silver halide color photographic light-sensitive material which does not discolor a cyan dye image for a long period of time, is particularly excellent in light fastness and has a high storability. Another object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent color reproducibility, little coloring of a white background even when a dye image is stored for a long period of time, and less loss of balance among the three colors of yellow, magenta and cyan. To provide the material.

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[0010]

[Chemical 2]

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[Chemical 3]

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More specifically, R ₃ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). , An alkynyl group, a cycloalkyl group, and a cycloalkenyl group, and specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (for example, 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group,
Carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butyl). Phenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3
-Methoxycarbamoylphenoxy), an acylamino group (for example, acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (eg, phenylamino, 2-chloroanilino) , 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2
-(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), a ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (for example, N, N-). Dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-).
t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, ,
Methanesulfonamide, hexadecanesulfonamide,
Benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5
t-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N.
-{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy). A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl Oxy carbonylamino group (e.g., phenoxycarbonylamino), an imido group (e.g., N- succinimido, N- phthalimido, 3
-Octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-diphenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl), and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

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[Chemical 19]

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[0155]

[Chemical 54]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Morigaki 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. At least one layer selected from cyan dye-forming couplers represented by the following general formula (I) or (II) on at least one layer on a support, and nickel is an oxygen atom, sulfur atom or nitrogen in an organic compound. A silver halide color photographic light-sensitive material comprising at least one nickel complex bonded or coordinated with an atom. [Chemical 1] (In formula, Za and Zb are -C (R < ₃ >) = or -N, respectively.
Represents =. However, one of Za and Zb is -N =
, And the other is -C (R ₃₎ is =. R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more, and the sum of σ _p values of R ₁ and R ₂ is 0.65 or more. R ₃ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. The group of R ₁ , R ₂ , R ₃ or X may be a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. )