JP2002287313A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having superior color developing properties, less liable to form a color mixture, excellent in hue and having good color reproducibility, a silver halide color photographic sensitive material giving a developed color image having high stability to light, heat, air, chemicals, etc., and a silver halide color photographic sensitive material having improved color developing property and processing stability of a pyrrolotriazole coupler. SOLUTION: Each of the silver halide color photographic sensitive materials contains at least one coupler of formula (CP) and at least one compound of formula (I) in at least one layer on the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material").

[0002]

2. Description of the Related Art In silver halide color light-sensitive materials,
Using the exposed silver halide as an oxidizing agent, an oxidized aromatic primary amine-based color developing agent reacts with a coupler (hereinafter, sometimes simply referred to as a coupler) to form indophenol, indoaniline, indamine, azomethine. ,
It is well known that dyes such as phenoxazine and phenazine are formed and images are formed. In this photographic method, a subtractive color method is used, and yellow, magenta,
A color image is formed by the cyan dye. Of these, phenol, naphthol-based couplers and the like have hitherto been used to form cyan dye images. However, the dyes formed from these couplers have an unfavorable absorption in the yellow to magenta region, and thus have a problem of deteriorating color reproducibility. It is rare.

As means for solving this problem, heterocyclic compounds described in US Pat. Nos. 4,728,598 and 4,873,138, and European Patent 0249453A2 have been proposed. However, these couplers have fatal drawbacks such as low coupling activity and poor dye fastness. As a coupler which overcomes these disadvantages, pyrrolotriazole couplers described in U.S. Pat. No. 5,256,526 and EP 0545300 have been proposed. These couplers are improved couplers in terms of hue and coupling activity.

However, when other layers such as a magenta dye image-forming layer and a yellow dye image-forming layer develop color, the cyan dye image-forming layer also develops a color, and the hue of the magenta dye image or the yellow dye image becomes turbid (mixed color). )
Sometimes. In order to solve this problem, hydroquinones described in U.S. Pat. No. 5,547,825, phenidones described in WO98 / 33760, WO00 / 23849, and JP-A-2000-122.
Studies have been made to solve the problem using various additives such as lactones described in No. 243. However, at present, these additive technologies have not sufficiently solved the above-mentioned problems.

On the other hand, improvement studies on pyrrolotriazole couplers have also been carried out, as disclosed in JP-A-9-189988 and JP-A-9-189988.
Japanese Patent Application No. 0-221825 and Japanese Patent Application No. 2000-282530 also describe a pyrrolotriazole coupler having a specific structure. However, these techniques do not sufficiently solve the above-mentioned problems, and do not satisfy other photographic performances. Therefore, studies on both additives and pyrrolotriazole couplers have been continued. In particular, further development of the technology was necessary in order to sufficiently bring out the characteristics of the dye having an excellent hue formed from the pyrrolotriazole coupler into the light-sensitive material.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent color reproducibility, low color mixing and excellent hue and excellent color reproducibility. A second object of the present invention is to provide a silver halide color photographic light-sensitive material having a color image having high stability to light, heat, air, chemicals and the like. A third object of the present invention is to provide a silver halide color photographic light-sensitive material having improved color development and development processing stability of a pyrrolotriazole coupler.

[0007]

The above object is achieved by the following means. That is, the present invention provides: <1> at least one layer on a support, the following general formula (C)
A silver halide color photographic light-sensitive material containing at least one kind of each of the coupler represented by P) and a compound represented by the following general formula (I).

[0008]

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[0009] (In the general formula (CP), each Z ^a and Z ^b -C (R ³⁾ = or represents -N =. However,
Z ^a, any of Z ^b, is -N =, the other is -C (R
³ ) = R ¹ and R ² are substituent constant sigma _p value of Hammett's each represent a 0.20 or more electron withdrawing groups, and R ¹
And the sum of Hammett's substituent constant σ _p value of 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 leaving in a coupling reaction with an oxidized form 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 form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. )

(In the general formula (I), R ^{21 to} R ²⁸ may be the same or different and each represents a hydrogen atom,
Or a substituent. R ²⁰ and R ²⁹ each represent a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. R ³⁰ represents an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an arylamino group. The group of R ^{20 to} R ³⁰ may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. )

<2> The silver halide color coupler according to <1>, wherein at least one of the couplers represented by the general formula (CP) is a coupler represented by the following general formula (). I-photosensitive material.

[0012]

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(In the general formula (CP-I), R ¹¹ , R
¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and each represents a hydrogen atom or a substituent, and Z is a non-metallic atom group necessary for forming a ring structure together with carbon atoms at both ends. And the group of nonmetallic atoms formed by Z may be substituted with a substituent. X ² represents a hydrogen atom or a substituent. R ¹⁶
Represents a hydrogen atom or a substituent. )

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
When a group in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated, unless otherwise specified. Group, alkenyl group, cycloalkyl group and cycloalkenyl group, which may be unsubstituted or have a substituent. When an aryl moiety is included, the aryl moiety may be a single ring or a condensed ring, and may be unsubstituted or have a substituent. When a heterocyclic moiety is included, the heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and may be a saturated ring.
It may be an unsaturated ring, a single ring or a condensed ring, and may be unsubstituted or have a substituent.

The substituent in the present specification may be any group that can be substituted, unless otherwise specified. Examples thereof include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, and an aliphatic group. Aliphatic oxy group, aryloxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyl Oxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group , Aliphatic oxycarbonylamino group, aryloxy Carbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group Carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group and the like.

The Hammett's substituent constant σp value in the present specification will be described briefly. Hammett's rule was introduced in 1935 in L. L. in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dea
n, "Lange's Handbook of Ch
mistry "12th edition, 1979 (Mc Gra
w-Hill) and “Region of Chemistry” special issue, No. 122, 96
Pp. 103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to the substituent having a value known in the literature, which can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett rule. Here, the compound represented by the general formula (CP) is not a benzene derivative, but the σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense in the future. The term “lipophilic” as used in the present invention means that the solubility in water at room temperature is 1%.
It is less than 0%.

(Silver halide color photographic light-sensitive material) In the silver halide color photographic light-sensitive material of the present invention, a coupler represented by the following formula (CP) and a coupler represented by the following formula (I) are provided on at least one layer on a support. ) Are contained at least one each. The silver halide color photographic light-sensitive material of the present invention has excellent color developability and low color mixing by using a coupler represented by the following formula (CP) and a compound represented by the following formula (I) in combination. Excellent color reproducibility with excellent hue, and high stability of the color image to light, heat, air, chemicals, etc. Further, the color development and development processing stability of the pyrrolotriazole coupler are improved.

[0018]

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[0019] In the general formula (CP), Z ^a and Z ^b each a -C (R ³⁾ = or represents -N =. Where Z ^a ,
One of Z ^b is -N =, and the other is -C (R ³ ) =
It is. R ¹ and R ² are Hammett's substituent constant σ, respectively.
represents an electron-withdrawing group having a _p- value of 0.20 or more, and R ¹ and R ²
The sum of Hammett's substituent constant σ _p value is 0.65 or more. R ³ represents a hydrogen atom or a substituent. X represents a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. R ¹ , R ² , R ³ or
The group of X may be a divalent group and form a homopolymer or a copolymer by bonding to a polymer or a polymer chain of a dimer or more.

In the general formula (I), R ^{21 to} R ²⁸ may be the same or different and each represents a hydrogen atom or a substituent. R ²⁰ and R ²⁹ are each a hydrogen atom,
It represents an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. R ³⁰ is an aliphatic oxy group,
Represents an aryloxy group, an aliphatic amino group, or an arylamino group. The group of R ^{20 to} R ³⁰ may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain.

Hereinafter, the coupler represented by formula (CP) will be described in detail. In the general formula (CP), Z ^a and Z ^b each a -C (R ³⁾ = or an -N =. However,
One of Z ^a and Z ^b are -N =, the other is -C
(R ³ ) =.

In the general formula (CP), R ³ represents a hydrogen atom or a substituent, and the substituent includes a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group,
Hydroxy group, nitro group, carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonyl Amino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio Group, sulfinyl group, phosphonyl group,
Examples include an aryloxycarbonyl group and an acyl group. These groups may be further substituted with the groups exemplified for R ³ .

In the general formula (CP), R ³ is more specifically a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), or an alkyl group (for example, having 1 to 32 carbon atoms).
Linear or branched alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl groups, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl , 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide}
Phenyldipropyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t
-Amylphenoxy) propyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-
t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), a cyano group, a hydroxy group, a 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-butylphenoxy, 3
-Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamide, tetradecaneamide, 2- (2,4-di-tert-amylphenoxy) butanamide, 4- ( 3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide, alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino ), Anilino groups (eg, phenylamino,
2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5
-{2- (3-tert-butyl-4-hydroxyphenoxy) dodecaneamide} anilino), a ureido group (eg, phenylureido, methylureide, N, N-dibutylureido), a sulfamoylamino group (eg,
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), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 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 Groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an 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), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl).

In the general formula (CP), R^ThreeAs preferred
Or an alkyl group, an aryl group, a heterocyclic group, a cyano
Group, nitro group, acylamino group, arylamino group, c
Raid group, sulfamoylamino group, alkylthio group,
Arylthio group, alkoxycarbonylamino group, sulf
Honamido group, carbamoyl group, sulfamoyl group,
Ruphonyl group, alkoxycarbonyl group, heterocyclic oxy
Group, acyloxy group, carbamoyloxy group, aryl
Oxycarbonylamino group, imide group, heterocyclic thio
Group, sulfinyl group, phosphonyl group, aryloxyca
Examples include a rubonyl group and an acyl group. R^ThreeAs further
Preferred are an alkyl group and an aryl group.
More preferably from at least one substituent
An alkyl group and an aryl group, more preferably
Alkyl, alkoxy, sulfonyl, sulfamoi
Group, carbamoyl group, acylamino group and sulfone
At least one selected from the group consisting of
Alkyl group or aryl group. R ^ThreeAs
Particularly preferably, an alkyl group, an acylamino group and
At least one selected from honamide groups is a substituent
An alkyl group or an aryl group. Ants
When these substituents are present in the
Is more preferably in the ortho or para position.

In the general formula (CP), R ¹ and R ² each represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more, and a Hammett's substituent constant σp of R ¹ and R ^2. The sum of the values is 0.65 or more. By doing so, the coupler represented by the general formula (CP) can develop a color as a cyan image. R ¹ and R ² are preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.30 or more, and have an upper limit of 1.0 or less. Further, the Hammett's substituent constant σp of R ¹ and R ²
The sum of the values is preferably 0.70 or more, and the upper limit is about 1.8.

In the general formula (CP), the σp value is 0.2
Specific examples of R ¹ and R ² which are 0 or more electron-withdrawing groups include acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono 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, σp
Examples include an aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with another electron-withdrawing group having a value of 0.20 or more. Among these substituents, the group which can have a further substituent may further have the group described for R ³ .

In the general formula (CP), the σp value is 0.2
More specifically, R ¹ and R ² which are 0 or more electron-withdrawing groups include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), carbamoyl Groups (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 (eg, methoxycarbonyl, ethoxycarbonyl,
iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl,
Butyloxycarbonyl, dodecyloxycarbonyl,
Octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (eg, diphenylphosphono), diarylphosphinyl Group (for example,
Diphenylphosphinyl), an alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl), an arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), an alkylsulfonyl group (eg,
Methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio, benzoylthio), sulfamoyl group (eg, N -Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, Thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), halogenated alkyl group (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy group (eg, trifluoromethyloxy) Halogenated aryloxy group (for example, pentafluorophenyloxy), halogenated alkylamino group (for example, N, N-di- (trifluoromethyl) amino), halogenated alkylthio group (for example, difluoromethylthio, 1,1 , 2,2-tetrafluoroethylthio), aryl groups substituted with another electron-withdrawing group having a σp of 0.20 or more (eg, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) , A heterocyclic group (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), a halogen atom (eg, a chlorine atom, a bromine atom) ), An azo group (eg, phenylazo) or a selenocyanate group. Among these, the group capable of having a substituent may further have the group as described for R ³ .

In the general formula (CP), R ¹ and R ² are preferably acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, aryl Sulfinyl group, alkylsulfonyl group,
Arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, halogenated aryloxy group, aryl group substituted with two or more other electron-withdrawing groups having a σp of 0.20 or more , And a heterocyclic group. R ¹ and R ² are 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 (especially a cycloalkoxycarbonyl group).

In the general formula (CP), a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent represents a halogen atom, Alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group Carbamoyloxy group, heterocyclic carbonyloxy group, 5- or 6-membered nitrogen-containing heterocyclic group, imide group, arylazo group and the like.
^It may be substituted with a group permitted as the substituent of ³ .

In the general formula (CP), X is more specifically a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy,
Carboxypropyloxy, methanesulfonylethoxy, ethoxycarbonylmethoxy), aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy) , 2-carboxyphenoxy), an acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), an alkyl or arylsulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino) , Heptafluorobutyrylamino), alkyl or arylsulfonamido groups (eg, methanesulfonylamino, trifluoromethanesulfonylamino p-toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), an alkyl, aryl or heterocyclic thio group (for example, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5
-T-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyl group (for example, N, N-diethylcarbamoyl, N-
Ethylcarbamoyl, N-ethyl-N-phenylcarbamoyl), a heterocyclic carbonyloxy group (for example, morpholinocarbonyloxy, piperidinocarbonyloxy), a 5- or 6-membered nitrogen-containing heterocyclic group (for example,
Imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl),
An imide group (for example, succinimide, hydantoinyl), an arylazo group (for example, phenylazo, 4-methoxyphenylazo) and the like can be mentioned. X may also take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom. X may contain a photographically useful group such as a development inhibitor and a development accelerator.

In the general formula (CP), X is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a hetero atom. A ring carbonyloxy group is a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom. X is more preferably a halogen atom, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and particularly preferably a carbamoyloxy group, a heterocyclic carbonyloxy group. Group.

In the general formula (CP), R ¹ , R ² , R ³
Alternatively, the group of X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. The homopolymer or copolymer bonded to the polymer chain is typically a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by the general formula (CP). In this case, the polymer may contain one or more types of cyan coloring repeating units having a coupler residue represented by the general formula (CP), and one of non-coloring ethylene type monomers as a copolymer component. Alternatively, a copolymer containing two or more kinds may be used. The cyan coloring repeating unit having a coupler residue represented by the general formula (CP) is preferably represented by the following general formula (P).

[0033]

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In the general formula (P), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom;
CONH-, -COO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and L represents -C
ONH-, -NHCONH-, -NHCOO-, -NH
CO-, -OCONH-, -NH-, -COO-, -O
CO -, - CO -, - O -, - S -, - SO 2 -, - N
Represents HSO ₂ — or —SO ₂ NH—. a, b, and c represent 0 or 1. Q is R of the compound represented by formula (CP)
¹ , represents a coupler residue from which a hydrogen atom has been removed from R ² , R ³ or X. As the polymer, a copolymer of a cyan color-forming monomer represented by a coupler unit represented by the general formula (CP) and a non-color-forming ethylene-like monomer that does not couple with an oxidation product of an aromatic primary amine developer is preferable.

The non-color-forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developer includes:
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, di- 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 (e.g., vinyl acetate, vinyl propion) Acrylates and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives such as vinyltoluene, divinylbenzene,
Vinyl acetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and- 4-vinylpyridine and the like. In particular, acrylates, methacrylates, and maleates are preferred.
The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the coupler represented by the general formula (CP) may be a copolymer formed as is well known in the field of polymer couplers. Physical and / or chemical properties of
For example, it can be selected such that the solubility, the compatibility of the photographic colloid composition with a binder such as gelatin, its flexibility, thermal stability and the like are favorably affected.

In order to incorporate the coupler represented by the general formula (CP) into the silver halide light-sensitive material, preferably into the red-sensitive silver halide emulsion layer, it is preferable to use a so-called inner type coupler. , R ¹ , R ² , R ³ , and X are preferably so-called ballast groups (preferably having a total carbon number of 10 or more).
More preferably, it is 50. In particular, it is preferable that R ² or R ³ has a ballast group.

The coupler represented by the general formula (CP) is more preferably a coupler represented by the following general formula (CP-I).

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In the general formula (CP-I), R ¹¹ ,
R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ may be the same or different and represent a hydrogen atom or a substituent, and Z is a nonmetallic atom group necessary for forming a ring structure together with carbon atoms at both ends. Represents
The group of nonmetal atoms formed by Z may be substituted with a substituent. X ² represents a hydrogen atom or a substituent. R ¹⁶ represents a hydrogen atom or a substituent.

Hereinafter, a cap represented by the general formula (CP-I)
Will be described in detail. In the general formula (CP-I),
R¹¹, R¹², R¹³, R¹⁴, R¹⁵Are the same but different
And each represents a hydrogen atom or a substituent. Place
As the substituent, a substituted or unsubstituted aliphatic group, or
A substituted or unsubstituted aryl group is preferred, and more preferred.
The following is a description of the new ones. R¹¹, R¹²
Preferably represents an aliphatic group, for example, having 1 to 1 carbon atoms
36 linear, branched or cyclic alkyl groups, aralkyl
Alkenyl, alkynyl, cycloalkenyl
Groups, for example, methyl, ethyl, propyl,
Isopropyl, t-butyl, t-amyl, t-octyl,
Represents tridecyl, cyclopentyl, cyclohexyl.
More preferably, the aliphatic group has 1 to 12 carbon atoms.
You. R¹³, R¹⁴, R¹⁵Is preferably a hydrogen atom or
Represents an aliphatic group. Preferably, the aliphatic group is
¹¹, R¹²And the groups mentioned above. R¹³, R¹⁴, R ¹⁵Is
Particularly preferred is a hydrogen atom.

In the general formula (CP-I), Z is
Non-metallic atoms required to form a ring structure with carbon atoms
A nonmetallic atom group (ring) formed by Z is a substituent
It may be substituted. The ring formed by Z is preferably
Is a 5- to 8-membered ring, and has an unsaturated bond even if it is a saturated ring.
You may have. Preferred non-metallic atoms include nitrogen
Atom, oxygen atom, sulfur atom or carbon atom,
More preferably, it is a carbon atom. Ring formed by Z
Are, for example, cyclopentane ring, cyclohexane
Ring, cycloheptane ring, cyclooctane ring, cyclohexene
Sene ring, piperazine ring, oxane ring, thiane ring, etc.
These rings are represented by R in the aforementioned general formula (CP).
^ThreeMay be substituted with a group represented by Shape with Z
The ring to be formed is preferably
A xan ring, and particularly preferably, the 4-position has 1-2 carbon atoms.
And an alkyl group represented by R 4 in the general formula (CP)^Threeso
May be substituted with a group represented by
Is a cyclohexane ring.

In the general formula (CP-I), R ¹⁶ represents a hydrogen atom or a substituent.
And the same as those described above for R ³ . R ¹⁶ is preferably an alkyl group or an aryl group, and more preferably a substituted aryl group. From the viewpoint of the number of carbon atoms, in the case of an alkyl group, the number is preferably 1 to 36, and in the case of an aryl group, the number of carbon atoms is preferably 6 to 36.
There are 36. Further, among the aryl groups, those in which the alkoxy group is substituted at the ortho position of the bond position with the coupler mother nucleus are not preferred because the light fastness of the dye derived from the coupler is low. In that respect, the substituent of the aryl group is preferably a substituted or unsubstituted alkyl group, and among them, an unsubstituted alkyl group is most preferred. Particularly, an unsubstituted alkyl group having 1 to 30 carbon atoms is preferable.

In the general formula (CP-I), X ² represents a hydrogen atom or a substituent. The substituent is preferably a group that promotes the elimination of the X ² —C (＝ O) O— group during the oxidative coupling reaction. X ² is preferably a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group.
The hetero ring is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom or a sulfur atom and having 1 to 36 carbon atoms. More preferably, a 5-membered or 6-membered bond through a nitrogen atom
Among them, a 6-membered ring is particularly preferred. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazoline and the like, preferably morpholine and piperidine, and particularly preferably morpholine. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the aforementioned substituents for R ³ , which further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), a chlorine atom,
It may be substituted with a hydroxyl group, a carboxyl group, or the like.
As the substituted amino group, disubstitution is preferable to monosubstitution. As the substituent, an alkyl group is preferable. The aryl group preferably has 6 to 36 carbon atoms, and more preferably has a single ring. Specific examples include phenyl, 4
-T-butylphenyl, 2-methylphenyl, 2,4
6-trimethylphenyl, 2-methoxyphenyl, 4-
Methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl and the like can be mentioned.

In the general formula (CP-I), from the viewpoint of the effect of the present invention, R ¹¹ and R ¹² are alkyl groups, and R ¹³ and R
^It is preferred that R ¹⁴ and R ¹⁵ are hydrogen atoms and R ¹⁶ is an aryl group, R ¹¹ and R ¹² are alkyl groups,
¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, R ¹⁶ is an aryl group, the ring formed by Z is a cyclohexane ring, and X ² is a 5- or 6-membered ring bonded by a nitrogen atom. Most preferred is a nitrogen-containing heterocycle or a dialiphatic substituted amino group.

The coupler represented by the general formula (CP-I) has an oil-solubilizing group in the molecule and is easily soluble in a high-boiling organic solvent. The coupler itself and the coupler and a color-forming reducing agent (developer) It is preferable that the dye formed by oxidative coupling between the dye and the dye is non-diffusible in the hydrophilic colloid layer. The coupler represented by the general formula (CP-I) is a compound represented by R ¹⁶
Contains a coupler residue represented by the general formula (CP-I) and forms a multimer or a dimer, or R ¹⁶ contains a polymer chain and is a homopolymer or copolymer. A coalescence may be formed. The homopolymer or copolymer having a polymer chain is typically an addition polymer having a coupler residue represented by the general formula (CP-I), homo- or copolymer of an ethylenically unsaturated compound. It is. In this case, one or more kinds of cyan coloring repeating units having a coupler residue represented by the general formula (CP-I) may be contained in the polymer, and an acrylic acid ester, a methacrylic acid ester, It may be a copolymer containing one or more non-color-forming ethylene-type monomers that do not couple with the oxidation product of an aromatic primary amine developer such as maleic esters.

Hereinafter, specific examples (exemplary compounds (1) to (47)) of the coupler represented by formula (CP) of the present invention will be shown, but it should not be construed that the invention is limited thereto.

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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The coupler represented by the general formula (CP) can be prepared by a known method, for example, as described in JP-A-5-150423 and JP-A-5-150423.
No. 255333, No. 5-202004, No. 7-483
No. 76 and 8-109172.

Hereinafter, specific examples of the synthesis of the cyan coupler represented by formula (CP) of the present invention will be described. It goes without saying that other exemplified compounds can be synthesized in the same manner.

Synthesis Example 1 Synthesis of Exemplified Compound (1)-Exemplified Compound (1) was synthesized by the following route.

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Synthesis of compound (b) 2,6-di-t-butyl-4-methylcyclohexanol, 17 g (75 mmol) of acetonitrile 200 m
trifluoroacetic anhydride at 0 ° C., 10.6 m
1 (75 mmol) was added dropwise, followed by slow addition of 15.6 g (60.4 mmol) of the compound (a). After the reaction solution was stirred at room temperature for 2 hours, water 300
ml and 300 ml of ethyl acetate were added and extracted. The organic layer was washed with aqueous sodium bicarbonate, water and brine. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 19.6 g of compound (b).

Synthesis of Compound (c) To a solution of 19.6 g of the compound (b) in 200 ml of ethyl acetate was added 5 ml of pyridine, and bromine was added dropwise under cooling with water. After stirring for 1 hour, water 300 ml, ethyl acetate 30
0 ml was added and extracted. After extraction, the ethyl acetate layer was dried over magnesium sulfate, the solvent was distilled off, and acetonitrile was added to the residue, followed by recrystallization. 18.0 g of compound (c)
Obtained.

Synthesis of compound (e) 2.2 g of methyl cyanoacetate in dimethylacetamide 20
0.8 g of sodium hydride was slowly added to the ml solution at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. (Solution S) 10.0 g of (c) dissolved in 50 ml of dimethylacetamide
Was slowly dropped into (Solution S) under ice-cooling. After stirring for 1 hour, 4 g of sodium hydroxide and 20 ml of methanol dissolved in 20 ml of water were added to the reaction solution, and the mixture was stirred for 1 hour while maintaining the reaction temperature at 50 ° C. After the reaction, 200 ml of ethyl acetate was added and neutralized with aqueous hydrochloric acid. After washing with water, the ethyl acetate layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude compound (e).

Synthesis of Exemplified Compound (1) 8.0 g of the obtained crude compound (e) was dissolved in 40 ml of dimethylacetamide and 6 ml of pyridine, and 4.3 g of morpholinocarbamoyl chloride was added at 0 ° C. After stirring at room temperature for 2 hours, the mixture was poured into 200 ml of diluted hydrochloric acid,
Extracted with 200 ml of ethyl acetate. After the organic phase was washed with water and dried over magnesium sulfate, the solvent was distilled off under reduced pressure.
Hexane was added to the residue, and crystallization was performed to obtain 6.0 g of the exemplary compound (1). Melting point: 256 ° C-257
° C.

Synthesis Example 2. Synthesis of Exemplified Compound (25)-In the synthesis of Exemplified Compound (1), 4.5 g of diallylcarbamoyl chloride was added instead of morpholinocarbamoyl chloride, and the mixture was stirred at room temperature for 2 hours. After the reaction, the mixture was poured into 200 ml of diluted hydrochloric acid, and 200 ml of ethyl acetate was added.
Extracted with l. After the organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and crystallization was performed, whereby 5.5 g of the desired Exemplified Compound (25) was obtained.
Obtained. Melting point: 219-220 ° C.

The coupler represented by the general formula (CP) is preferably contained in a silver halide emulsion layer, and the amount of silver in the emulsion layer can take any value with respect to the coupler. From the viewpoint of color development and color reproducibility, preferably 2.
0 to 8.0, more preferably 2.8 to 6.0
Or less, most preferably 2.8 or more and 5.0 or less. Here, the ratio of silver to the coupler is defined by the molar conversion ratio of silver to the coupler. The coupler represented by the general formula (CP) is provided on a support, generally in a range of 0.01 to 1;
g / m ^2, preferably not 0.05 to 0.4 g / m ^2, more preferably preferably it is applied in an amount of 0.1 to 0.3 g / m ^2.

The coupler represented by the general formula (CP) has p
In a conventional color light-sensitive material containing a phenylenediamine as a color developing agent, it is useful as a cyan coupler, but can be contained in any light-sensitive silver halide emulsion layer. Also, in a system using a color developing agent other than p-phenylenediamines, it is useful as a dye-forming coupler for giving dyes of various hues.

Hereinafter, the compound represented by formula (I) will be described in detail. In the general formula (I), R ^{21 to} R ²⁸ each represent a hydrogen atom or a substituent, and the substituent includes a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, Carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group,
Arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group,
Examples include a silyloxy group, a sulfonyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may be further substituted with substituents as exemplified for R ²¹ .

In the general formula (I), R ^{21 to} R ²⁸ are more specifically a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an aliphatic group (for example, having 1 to 3 carbon atoms).
2 straight-chain or branched-chain alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonyl Ethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamido} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, Cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl) , A heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 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, -Methanesulfonylethoxy), an aryloxy group (e.g., phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamide, tetradecaneamide, 2- (2,4-di-tert-amylphenoxy) butanamide, 4- ( 3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide, alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino ), Arylamino groups (eg, anilino,
2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5
-{2- (3-tert-butyl-4-hydroxyphenoxy) dodecaneamide} anilino), a ureido group (eg, phenylureido, methylureide, N, N-dibutylureido), a sulfamoylamino group (eg,
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), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 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 Groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (eg,
Methanesulfonyloxy, octanesulfonyloxy,
Benzenesulfonyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino),
Imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-
Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), and an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

In the general formula (I), R ^{21 to} R ²⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acylamino group, an arylamino group, a ureido group, Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, acyloxy group, carbamoyloxy group,
Examples include a sulfonyloxy group, an aryloxycarbonylamino group, and an aryloxycarbonyl group. R ²¹ ~
R ²⁸ is more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an acyloxy group, a sulfonyloxy group, or an alkoxycarbonyl group. Most preferably, R ^{21 to} R ²⁸ are a hydrogen atom, an alkyl group, an alkoxy group,
This is the case where both R ²¹ and R ²⁷ are substituted with an alkyl group or an alkoxy group.

In the general formula (I), R ²⁰ and R ²⁹ each represent a hydrogen atom or an aliphatic group (for example, having 1 to 32 carbon atoms).
Linear or branched alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl , 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide}
Phenyldipropyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t
-Amylphenoxy) propyl), an acyl group (e.g.,
Acetyl, benzoyl, 4-methylbenzoyl), 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 Groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), aliphatic oxycarbonyl groups (eg, alkoxycarbonyl group, cycloalkoxycarbonyl group, specifically methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbo) D , Octadecyloxycarbonyl), an aryloxy carbonyl group (e.g., phenoxycarbonyl).

In the general formula (I), R ²⁰ and R ²⁹ are preferably a hydrogen atom, an alkyl group, a sulfonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and more preferably a hydrogen atom or an alkyl group. Preferably, R ²⁰ or R ²⁹ is more preferably when one of them is a hydrogen atom, and most preferably when both R ²⁰ or R ²⁹ are a hydrogen atom.

In the general formula (I), R ³⁰ is an aliphatic oxy group (for example, an alkoxy group, an alkenyloxy group, a cycloalkyloxy group, specifically, for example, methoxy, butoxy, dodecyloxy, methoxyethoxy, cyclohexyloxy) An aryloxy group (for example, phenoxy, 4-chlorophenoxy), an aliphatic amino group (for example, an alkylamino group, a dialkylamino group, a dicycloalkylamino group, and a dialkenylamino group; Amino, dioctylamino, dicyclohexylamino, diallylamino) and arylamino groups (for example, anilino, 4-anisidino, N-methylanilino).

In formula (I), R ³⁰ is preferably an alkoxy group, an alkylamino group, a dialkylamino group or an arylamino group, and more preferably an alkoxy group, a dialkylamino group or an arylamino group. .

The compound represented by the general formula (I) preferably has an oil-solubilizing group in the molecule, is easily dissolved in a high-boiling organic solvent, and is preferably non-diffusible in the hydrophilic colloid layer. In this respect, the total number of carbon atoms is preferably 16 to 60, and more preferably 18 to 50.

[0082] compound represented by formula (I), R ²⁰
~ R ³⁰ contains a compound residue represented by the general formula (I) and forms a dimer or more multimer, or contains a polymer chain and forms a homopolymer or copolymer It may be. A typical example of the homopolymer or copolymer containing a polymer chain is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a compound residue represented by the general formula (I). In this case, the repeating unit having the compound residue represented by the general formula (I) contains 1 unit in the polymer.
One or more non-color-forming ethylene-type monomers which do not couple with oxidation products of aromatic primary amine developing agents such as acrylic acid esters, methacrylic acid esters, and maleic acid esters.
It may be a copolymer containing one or more species.

In the general formula (I), R ²¹ and R ²⁷ are a hydrogen atom or an alkyl group, R ²⁰ and R ²⁹ are a hydrogen atom or an alkyl group, R ³⁰ is an alkoxy group,
R ²¹ and R ²⁷ are preferably a hydrogen atom or an alkyl group, R ²⁰ and R ²⁹ are hydrogen atoms, and R ³⁰ is an alkoxy group, a dialkylamino group, or a dialkylamino group or an arylamino group. Most preferred is an arylamino group having a total carbon number of 18 to 50.

Hereinafter, specific examples of the compound represented by formula (I) of the present invention (exemplified compounds (I-1) to (I-32))
But are not limited to these.

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Compounds represented by the general formula (I) can be prepared by known methods, for example, as described in JP-A-62-262047, world patents WO00 / 23849 and JP-A-2000-12224.
The compound can be synthesized by the method described in Japanese Patent Publication No. 3 or a method analogous thereto.

Hereinafter, a synthesis example of the compound represented by the formula (I) will be described. -Synthesis example. Synthesis of Exemplified Compound (I-1) -2,6-dimethylphenol 25 g (0.205 mol)
Of glyoxylic acid ethyl ester polymer type 50% toluene solution in 20.9 g (0.103
Mol) and 1 ml of methanesulfonic acid at 40 ° C. with stirring.
Was added and stirred at 40 ° C. for 3 hours. 200 m of reaction solution
The mixture was poured into ice water and extracted with 200 ml of ethyl acetate. The ethyl acetate layer was washed twice with 200 ml of saturated saline and dried over magnesium sulfate. After magnesium sulfate was filtered off, the ethyl acetate layer was concentrated under reduced pressure, and crystallized from ethyl acetate / hexane = 1/1. The obtained crystals were recrystallized from ethyl acetate / hexane = 1/1 to give Exemplified Compound (I-1).
7.5 g were obtained. 81.8% yield, melting point 155-157 ° C.

The compound represented by the general formula (I) is used in combination with the coupler represented by the general formula (CP), and may be added to either the photosensitive layer or the non-photosensitive layer of the support. It is preferably added to the layer containing the coupler, and most preferably added to the layer containing the coupler represented by formula (CP) from the viewpoint of the effects of the present invention.

When the compound represented by the general formula (I) is added to the non-photosensitive layer, the amount thereof is
To 400% by mass, preferably 20 to 30% by mass.
0 mass% is more preferable, and 50 to 200 mass%.
When it is added to the photosensitive layer, it is most preferably 1 to 100% by mass, more preferably 1 to 50% by mass, more preferably 1 to 30% by mass. Some are most preferred.

The silver halide color photographic light-sensitive material of the present invention preferably further contains a compound represented by the following formula (A) from the viewpoint of the color image fastness of a color dye obtained from a coupler.

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In the general formula (A), L represents a single bond or an arylene group. R _a1 , R _a2 and R _a3 may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R _a1 further represents a radical (·) when L is a single bond, and R _a3 further represents a hydrogen atom. _Ra1 and L, _Ra2 and L, _Ra3 and L, _Ra1 and _Ra2 , _Ra2 and _Ra3, and _Ra1 and _Ra3 may combine with each other to form a 5- to 7-membered ring)

Hereinafter, the compound represented by formula (A) will be described in detail.
This will be described in detail. In the general formula (A), L is a single bond or
Is an arylene group (preferably having 6 to 36 carbon atoms, e.g.
(Enylene, naphthylene). R_a1, R_a2And R_a3
May be the same or different, and each represents an alkyl group
(Preferably a straight-chain, branched or cyclic C1-C36
Alkyl groups such as methyl, ethyl, isopropyl,
t-butyl, cyclohexyl, octyl, sec-oct
Chill, t-octyl, decyl, dodecyl, i-trideci
Le, tetradecyl, hexadecyl, octadecyl) al
Kenyl group (preferably a straight chain having 2 to 36 carbon atoms, branched or
Is a cyclic alkenyl group such as vinyl, allyl, cyclo
Rohexenyl, oleyl), aryl group (preferably charcoal
A prime number of 6 to 36, for example, phenyl, naphthyl) or f
A telocyclic group (preferably having 0 to 36 carbon atoms,
And a 5- to 7-membered ring containing at least one of N, O, S and P
Heterocyclic groups such as thienyl, furyl, and pirani
Le, pyrroyl, imidazolyl, indolyl, chroma
, Piperidinyl). R _a1Is the field where L is a single bond
In the case, it further represents a radical (•). R_a3Is a hydrogen source
Represents a child. R_a1And L, R_a2And L, R_a3And L, R_a1When
R_a2, R_a1And R_a3And R_a2And R _a3Are connected to each other 5
A 7-membered ring may be formed.

Each group in the general formula (A) may be further substituted with a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group. Group, hydroxyl group, alkoxy group, alkenoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, alkenylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, alkenylamino group, arylamino group, Heterocyclic amino group, acylamino group, sulfonamide group, acyl group, acyloxy group, alkoxycarbonyl group, alkenoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, sulfonyl group, sulfinyl group, alkoxycarbonylamino group,
Alkenoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group,
Examples include a carbamoyl group, a sulfamoyl group, a ureido group, a sulfonyloxy group, a carbamoyloxy group, a sulfamoyloxy group, a silyloxy group, a phosphoryloxy group, and a silyloxy group. The compound of the general formula (A) may form a bis-form or a tetra-form, and may further form a multimer (for example, a polymer linked to a polymer chain).

In the general formula (A), L is preferably a single bond or a phenylene group, more preferably a single bond. Preferably, all of R _a1 , R _a2 and R _a3 are an alkyl group or an alkenyl group. Also,
R _a1, R _a2, the sum of R _a3, L the number of carbon atoms thereof is preferably 10 or more and further preferably 15 or more. More preferred in the general formula (A) is the following general formula (A)
-I).

[0103]

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In the general formula (AI), R _a1 is the same as in the general formula (A). Z _a1 is a divalent group in which both of the two atoms bonding to N are carbon atoms, and
Represents a group of nonmetallic atoms necessary to form a 7-membered ring. L
_a1 represents a single bond or a phenylene group.

Of the compounds represented by the general formula (AI), most preferably the following general formula (A-II) or (A
-III).

[0106]

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In formulas (A-II) and (A-III), R _a1 is the same as in formula (A). R _a4 represents an alkyl group, an alkenyl group or a radical (·), and R _a5 represents a substituent. n represents an integer of 0.1 to 4. Z _a2 is 6
Represents a group of non-metallic atoms necessary for forming a member ring. Z _a1 is the same as in the general formula (AI).

[0108] When in the formula (A-II) is a group necessary for Z _a2 to form a piperidine ring. In the general formula (A-III), those in which R _a1 is an alkyl group or an alkenyl group, and those in which the R _a1 —O— group and the ring containing N and Z _a1 are in para-position to each other are preferable. . Formula (A-II) or (A-II)
Among the compounds represented by I), particularly, compounds represented by the general formula (A-II)
Is most preferable. In addition, those in which R _a4 is a radical (•) are preferable in that a small amount thereof exhibits a high effect.

Hereinafter, specific examples of the compound represented by formula (A) (exemplified compounds A- (1) to A- (58)) are shown, but the invention is not limited thereto.

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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The compound represented by the formula (A) is described in, for example, Japanese Patent Publication No. 6-75175, JP-A-1-132562.
No. 1,113,368, U.S. Pat. No. 4,921,9
Compounds can be synthesized according to the methods described in JP-A Nos. 62, 4,639, 415 and the like.

The compound represented by formula (A) is used in combination with a coupler represented by formula (CP).
The coupler may be added to either the photosensitive layer or the non-photosensitive layer of the support, but is preferably added to a layer containing a coupler. From the viewpoint of the effect of the present invention, the coupler represented by formula (CP) Most preferably, it is added to the containing layer.

The amount of the compound represented by formula (A) is preferably from 10 to 400% by mass, more preferably from 20 to 300% by mass, and more preferably from 50 to 200% by mass, based on the coupler. Is most preferred.

In the silver halide color photographic light-sensitive material of the present invention, in order to further improve the storability of the dye image, various organic and metal complex-based fadings other than the compound represented by the formula (A) are used. Inhibitors can also be used in combination. Organic discoloration inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromans,
There are alkoxyanilines, heterocycles, etc., and metal complexes include nickel complexes, zinc complexes and the like.
Page left column, No. 36544, 527 pages, No. 3071
No. 15,162, No. 15, pp. 872.

As the organic fading inhibitor, those disclosed in the following patent publications are preferred. As the aromatic compound,
The general formula (I) of JP-B-63-50691 and the general formulas (IIIa) and (III) of JP-B-2-37575.
b) (IIIc), the general formula of JP-A-2-50457,
The general formula of JP-A-5-67220, the general formula (IX) of JP-A-5-70809, the general formula of JP-A-6-19534, the general formula (I) of JP-A-62-227889, and the formula of JP-A-6-227889
General formulas (I) and (II) of JP-A-244046, General formulas (I) and (II) of JP-A-2-66541, and
139544, the general formulas (II) and (III), and
General formulas (I) and 2-2128 of JP-A-194062
No. 36, General formulas (B), (C), (D) and 3-200
758, Formula (III), and 3-48845, Formulas (II) and (III), and 3-266736.
Formulas (B), (C), (D), and 3-9694
No. 40, General formula (I) of JP 4-330440, General formula (I) of JP 5-297541, General formula of JP-A-6-130602, WO91
General formulas (1), (2) and (3) of DE / 11749, DE
General formula (I) of US Pat. No. 4,008,785 A1, US Pat.
No. 4,931,382, the general formula (II), EP-
General formula (a) in JP 203746B1, EP-264
730B1 is a compound represented by the general formula (I) and the like.

As the cyclic amine compound, Japanese Patent Publication No.
General formula (I) of JP-A-32298, General formula (I) of JP-A-3-39296, General formula of JP-A-3-40373, General formula (I) of JP-A-2-49762, and
General formulas (II) and 2-217 of JP-A-208063
No. 845, General Formula (III), US Pat.
555, General formula (B), EP-309400A2
No. 309401A1;
It is a compound represented by the general formula and the like in JP-A-309402A1.

As the amine compound, Japanese Patent Publication No. 6-97
332, formula (I), JP-B-6-97334, formula (I), JP-A-2-14837, formula (I) and JP-A-150841, formula (I). General formula (I) of JP-A-2-181145, General formula (I) of JP-A-3-266736, JP-A-4-350
Compounds represented by the general formula (IV) of JP-A 854 and the general formula (I) of JP-A-5-61166. Examples of the thioether compound include the general formula (I) of JP-B-2-44052, the general formula (T) of JP-A-3-48242,
JP-A-3-26636, Formula (A) and 5-32
General formulas (I), (II) and (III) of JP-A-3545, General formula (I) of JP-A-6-148837, US Pat.
No. 33,271, which is a compound represented by general formula (I) or the like. Examples of the phosphorus compound include JP-A-3-25437.
The general formula (I) of JP-A No. 3-142444, the general formula of US Pat. No. 4,749,645, the general formula of US Pat. No. 4,980,275, and the like. Compounds.

In addition to these compounds, alkene compounds represented by general formula (I) in US Pat. No. 4,713,317, boron compounds represented by general formula (I) in JP-A-4-174430,
Epoxy compounds of the general formula (II) of US Pat. No. 5,183,731, JP-A-8-53431, and general formula (S1) of a disulfide compound EP-271322
B1; the general formulas (I), (II), (III) and (IV) of JP-A-4-19736; the sulfinic acid compound represented by the general formula (1) of US Pat. No. 4,770,987; Compounds represented by the general formulas (I), (II), (III) and (IV) in U.S. Pat. No. 5,242,785, and the cyclic phosphorus compounds represented by the general formula (1) in JP-A-8-283279 Is also effective.

Further, metal complexes are also effective, and many dithiolate-based nickel complexes, salicylaldoxime-based nickel complexes and the like are known and effective.
No. 3736, the general formula (I) and JP-B-61-1373.
7, the general formula (I) of JP-B-61-13737, the general formula (I) of JP-B-61-13939, and the general formula (I) of JP-B-61-13740. ), The general formula (I) of JP-B-61-13742, the general formula (I) of JP-B-61-13743, the general formula (I) of JP-B-61-13744, and Japanese Patent Publication No. 5-69212. General formula of the gazette, 5-
JP-A-88809 discloses general formulas (I) and (II);
-199248, General formulas (I) and (II) of JP-A 64-75568, and JP-A-3-182749.
Formulas (I) and (II) described in US Pat.
No. 0,153, the general formulas (II), (III) and (I)
V), (V), and general formulas (II), (III), and (IV) described in JP-A-4,912,027 are more effective.

In the silver halide color photographic light-sensitive material of the present invention, the coupler represented by the general formula (CP-I), the compound represented by the general formula (A), and other compounds are prepared by a known dispersion method. Can be introduced into the photosensitive material by dissolving in a high boiling organic solvent (low boiling organic solvent can be used in combination)
An oil-in-water dispersion method in which the emulsion is dispersed in an aqueous gelatin solution and added to the silver halide emulsion is preferably used.

Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the latex dispersion method as one of the polymer dispersion methods are disclosed in U.S. Pat. No. 4,199,363, West German Patent (OLS) No. 2,541,274, and Japanese Patent Publication No.
No. 41,091, EP0727703A1, EP07
27704A1 and the like. Furthermore, a dispersion method using an organic solvent-soluble polymer is disclosed in PCT International Publication No. W
O88 / 723.

Examples of high-boiling organic solvents usable in the oil-in-water dispersion method include phthalic esters (eg, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate), phosphoric acid and phosphonic acid esters (Triphenyl phosphate, tricresyl phosphate, tri-2 phosphate
-Ethylhexyl, etc.), fatty acid esters (di-2-ethylhexyl succinate, tributyl citrate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, etc.), amides (N, N-diethyldodecaneamide) , N, N-dimethyloleinamide, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), anilines (N, N-dibutyl-2-butoxy-5-tert)
-Octylaniline, etc.), chlorinated paraffins, hydrocarbons (dodecylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (2- (2,4-di-tert-amylphenoxy) butyric acid, etc.) An organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethylformamide, etc.) may be used in combination as the solvent. It is preferably used in an amount of 0 to 10 times, preferably 0 to 4 times the ratio.

Further, the emulsified dispersion may be used, if necessary, from the viewpoint of improving the aging stability during storage in the state of the emulsified dispersion, suppressing the change in photographic performance and improving the aging stability of the final coating composition mixed with the emulsion. Thus, all or a part of the auxiliary solvent can be removed by a method such as distillation under reduced pressure, washing with noodles or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. Average particle size is Coulter Submicron Particle Analyzer model N4 (Coulter Electronics)
And the like.

The silver halide color photographic light-sensitive material of the present invention comprises at least one of a coupler represented by formula (CP) and a compound represented by formula (I).
It is sufficient that at least one seed-containing layer is provided on the support, and the coupler is contained in a hydrophilic colloid layer comprising a usual gelatin binder. A general light-sensitive material can be constituted by coating a support with at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one red-sensitive silver halide emulsion layer. The order may be any order. Further, an infrared-sensitive silver halide emulsion layer can be used instead of one of the above-mentioned photosensitive emulsion layers. These light-sensitive emulsion layers contain a silver halide emulsion that has sensitivity in each wavelength range and a coupler that forms a dye that has a complementary color relationship with the light to be exposed, so that color reproduction by the subtractive color method can be performed. Can be. However, the photosensitive emulsion layer and the color hue of the coupler may not have the above correspondence.

In the silver halide photographic light-sensitive material of the present invention,
In addition, conventionally known photographic materials and additives can be used. For example, a transmission type support or a reflection type support can be used as the support. Examples of the transparent support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers, and contains a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable. The water-resistant resin layer preferably contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent is used. More preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening material is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass relative to the resin, and more preferably 0.1 to 3% by mass.
001 to 0.5% by mass.

The reflective support may be a transmissive support or the above-described reflective support provided with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface. A more preferred reflective support is one having a polyolefin layer having micropores on the paper substrate on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer preferably adjacent to the gelatin layer on the side of the silver halide emulsion layer has no microvoids (for example, polypropylene, polyethylene) and is close to the paper substrate. More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of these multilayers or monolayers of polyolefin between the paper substrate and the photographic component layer is 0.40
To 1.0 g / ml, preferably 0.50 to 1.0 g / ml.
0.70 g / ml is more preferred. Further, the thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably from 10 to 100 μm,
5 to 70 μm is more preferred. Further, the ratio of the thickness of the polyolefin layer and the paper substrate is preferably 0.05 to 0.2,
0.1-0.5 is more preferable. Further, it is also preferable to provide a polyolefin layer on the opposite side (back side) of the paper base from the photographic component layer, from the viewpoint of increasing the rigidity of the reflective support. Polyethylene or polypropylene is preferred, and polypropylene is more preferred. The polyolefin layer on the back side preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm, and further preferably has a density of 0.7 to 1.1 g / ml. In the reflection support of the present invention, preferred embodiments relating to a polyolefin layer provided on a paper substrate are described in JP-A-10-333277 and JP-A-10-333.
No. 278, JP-A-11-52513, JP-A-11-6
Nos. 5024, EP0880065, and EP0880
066 is mentioned.

The silver halide grains in the silver halide emulsion are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded apex,
(It may have a higher-order plane.) Or octahedral crystal grains, or tabular grains having an aspect ratio of 2 or more composed of {100} planes or {111} planes in which 50% or more of the total projected area is preferred. . The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, cubic or tabular grains having a {100} plane as a principal plane or tabular grains having a {111} plane as a principal plane are preferably applied.

As the silver halide emulsion, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like are used.
From the viewpoint of rapid processing, a silver chloride or silver chlorobromide emulsion having a silver chloride content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The silver bromide localized phase (rich phase) is preferably formed by epitaxially growing a localized phase of at least 10 mol% or more in total silver bromide content in the silver bromide rich phase. The silver bromide content of the silver bromide-rich phase is preferably in the range of 10 to 60 mol%, most preferably in the range of 20 to 50 mol%. The silver bromide rich phase is preferably composed of 0.1 to 5 mol% of silver, preferably 0.3 to 4 mol% of the total silver constituting the silver halide grains. Is more preferable. The silver bromide rich phase contains IrC
preferably contains a Group VIII metal complex ion l ₆ ^3- and the like.

In the silver halide emulsion, various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. Examples of the compound to be used include iron, iridium, ruthenium, osmium, rhenium, rhodium, cadmium, zinc, lead, copper, thallium and the like, or a salt of a group VIII metal of the periodic table or a complex salt. it can. In the present invention, a metal compound having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, is particularly preferred in that it further enhances high illuminance sensitivity and suppresses latent image sensitization. In addition, an iridium compound also has an enormous effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably 10 ^{-9 to} 1 mol of silver halide.
Preferred is 10 to 10 ^-2 mol.

The silver halide emulsion is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column, are preferably used. Among them, it is particularly preferable that the metal is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates, gold thiosulfates, and gold colloids can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there. In the present invention, gold sensitization may be combined with other sensitization methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The silver halide color photographic light-sensitive material of the present invention has at least one layer each of a yellow-forming silver halide emulsion layer, a magenta-forming silver halide emulsion layer, and a cyan-forming silver halide emulsion layer. Preferably, The silver halide emulsion layer containing the yellow coupler may be located at any position on the support. However, when the yellow coupler containing layer contains silver halide tabular grains, the silver halide emulsion layer containing the magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the silver emulsion layer and the cyan coupler-containing silver halide emulsion layer. Also, promote color development, desilvering,
From the viewpoint of reducing the residual color due to the sensitizing dye, the silver halide emulsion layer containing the yellow coupler is preferably provided at a position farthest from the support than other silver halide emulsion layers. Further, from the viewpoint of reduction of Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of the other silver halide emulsion layers. The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055 and JP-A-9-114035
No. 10-246940, U.S. Pat.
No. 159, etc., a coupler layer containing no silver halide emulsion is provided adjacent to the silver halide emulsion layer,
It is also preferable to form a coloring layer.

In the silver halide color photographic light-sensitive material of the present invention, a reflective support, a silver halide emulsion, and a heterometallic ion species doped in silver halide grains;
Storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization methods (sensitizers), spectral sensitization methods (spectral sensitizers), cyan, magenta, yellow couplers and their emulsion dispersion methods,
The color image storability improver (anti-stain agent and anti-fading agent), dye (colored layer), gelatin type, layer constitution of photosensitive material, coating pH of photosensitive material, etc. are described in Tables 1-2 patents. Can be preferably applied to the present invention.

[0142]

[Table 1]

[0143]

[Table 2]

In the silver halide color photographic light-sensitive material of the present invention, the cyan, magenta and yellow couplers to be used in combination are described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column. 6th line, page 3, upper right column, line 14 to page 18, upper left column last line, and page 30, upper right column, line 6 to page 35, lower right column 11 of JP-A-2-33144.
Line and from page 0, line 15 of EP 0355,660A2
The couplers described on line 27, page 30, line 30 to page 28, line 45, line 29 to line 31, page 47, line 23 to page 63, line 50 are also useful. In addition, WO98 / 33760
Formulas (II) and (III) of JP-A-10-221
A compound represented by the general formula (D) of No. 825 may be added, which is preferable.

In the silver halide color photographic light-sensitive material of the present invention, it is preferable to use an antibacterial / antifungal agent. As the antifungal / antifungal agent, those described in JP-A-63-271247 are useful. It is. Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The silver halide color photographic light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a usual negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular,
A cathode ray tube which emits white light by mixing these light emitters is often used. When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, a plurality of colors are exposed to the cathode ray tube. May be input to emit light from the tube surface. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film that cuts a color other than the color (plane sequential exposure) may be employed. But,
Since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

The silver halide color photographic light-sensitive material of the present invention includes a gas laser, a light emitting diode, a semiconductor laser,
A digital scanning exposure method using monochromatic high-density light such as a semiconductor laser or a second harmonic emission light source (SHG) in which a non-linear optical crystal is combined with a solid-state laser using a semiconductor laser as an excitation light source is preferably used. To make the system compact and inexpensive, semiconductor lasers,
It is preferable to use a second harmonic generation light source (SHG) in which a semiconductor laser or a solid-state laser and a nonlinear optical crystal are combined. Particularly, in order to design an apparatus which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The maximum wavelength of the spectral sensitivity of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the light source for scanning exposure to be used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. When the exposure time in such scanning exposure is defined as a time for exposing a pixel size when the pixel density is 400 dpi, a preferable exposure time is 10 ^-4 seconds or less, more preferably 1 ^-4 seconds or less.
0 ^-6 seconds or less.

Preferred scanning exposure methods applicable to the silver halide color photographic light-sensitive material of the present invention are described in detail in the patents listed in Tables 1 and 2. In order to process the silver halide color photographic light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355. The processing materials and processing methods described on page 17, upper left column, line 17 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The silver halide color photographic light-sensitive material of the present invention is preferably applied to light-sensitive materials having rapid processing suitability. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called in-solution time) and the time when the photosensitive material leaves the color developing solution and is bleached and fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (the so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called in-solution time). The color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and still more preferably 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less, 6 seconds or more, and more preferably 3 seconds or less.
It is less than 0 seconds and more than 6 seconds. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less.
It is less than second and more than 6 seconds.

The method for developing the silver halide color photographic light-sensitive material of the present invention after exposure is a conventional method of developing with a developing solution containing an alkali agent and a developing agent, a method of incorporating the developing agent into the photographic material, In addition to wet methods such as developing with an activator solution such as an alkaline solution that does not contain
A heat development method without using a processing liquid can be used. In particular, since the activator method does not contain a developing agent in the processing solution, it is easy to manage and handle the processing solution, and is a preferable method from the viewpoint of environmental conservation because it has a small load when processing the waste liquid. In such an activator method, as the developing agent or its precursor incorporated in the photosensitive material, for example, JP-A-8-234388 and JP-A-9-1384 can be used.
No. 52686, No. 9-152693, No. 9-2118
The hydrazine-type compounds described in Nos. 14 and 9-160193 are preferred.

For the silver halide color photographic light-sensitive material of the present invention, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, JP-A-8-29735
No. 4, No. 9-152695, an image forming method using an activator liquid containing hydrogen peroxide is preferably used. In such an activator method,
Desilvering is usually performed after processing with an activator solution.However, in the image amplification processing method using a low-silver amount photosensitive material, desilvering processing should be omitted, and simple methods such as washing or stabilization should be performed. Can be. Further, in a method of reading image information from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution, known materials and processing methods can be used. Preferably, Research Disclosure Item 36544 (September 1994)
Mon) pages 536 to 541, JP-A-8-234388
Those described in the item can be used.

Incidentally, the silver halide color photographic light-sensitive material of the present invention includes not only a light-sensitive material for forming a color image but also a light-sensitive material for forming a monotone image including a black and white image. Further, the coupler represented by the general formula (CP) can be prepared by using a photosensitive material for an advanced photo system having a magnetic recording layer, a photosensitive material for a system for heating and developing using a small amount of water, and using no water. The present invention can be suitably applied to a photosensitive material for a complete dry system in which heat development is performed. These systems are described in JP-A-6-35,118 and JP-A-6-35118.
-17,528, JP-A-56-146,133, JP-A-60-119,557, JP-A-1-161,236 and the like.

[0155]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these embodiments. (Example 1) A corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Samples (001) of a silver halide color photographic light-sensitive material having the following layer constitution were prepared by sequentially coating seven photographic constituent layers. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 190 g of cyan coupler (ExC-2), 44 g of cyan coupler (ExC-3), 900 g of gelatin, 44 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-6) 7
3 g, 29 g of color image stabilizer (Cpd-7), 58 g of color image stabilizer (Cpd-9), 1 color image stabilizer (Cpd-10)
5 g, color image stabilizer (Cpd-14) 15 g, color image stabilizer (Cpd-15) 44 g, color image stabilizer (Cpd-16)
73 g of a color image stabilizer (Cpd-17) and 88 g of a color image stabilizer (Cpd-19) were added to a solvent (Solv-5) 2.
19 g, solvent (Solv-8) 146 g, solvent (Sol
v-9) dissolved in 73 g and 250 ml of ethyl acetate,
This liquid was emulsified and dispersed in 6,500 g of a 10% aqueous gelatin solution containing 200 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having a mean grain size of 0.41 μm (silver molar ratio). , Respectively, 0.09 and 0.11 for each size emulsion.
5 mol% was locally contained on a part of the surface of silver chloride-based grains). This emulsion contains the red-sensitive sensitizing dyes G and H shown below in large emulsion C per mole of silver.
Is 9.0 × 10 ^-5 mol per mol respectively for each 6.0 × 10 ^-5 mol to the small size emulsion C for. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 or Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2, 5.0
It was added as a mg / m ² and 10.0 mg / m ^2.

[0158]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0160]

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(Sensitizing dyes A, B and C were converted to silver halide 1
Per mole, 1.4 × 1 for large size emulsions
^0-4 moles, 1.7 × 1 each for small size emulsions
^0-4 moles were added. Green sensitive emulsion layer

[0162]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole was added. )

Red-sensitive emulsion layer

[0165]

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(The sensitizing dyes G and H were used in an amount of 6.0 × 10 5
^-5 mol, 9.0 × 10 for small size emulsion
^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0167]

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Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 5 per mol of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Further, each of the second layer, the fourth layer, the sixth layer and the seventh layer has a thickness of 0.2 m.
g / m ² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1
mg / m ² . 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 per mol of silver halide. 2 × 10 ^-4
Mole was added. Further, 0.05 g / m ² of a copolymer of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000 to 400,000) was added to the red-sensitive emulsion layer. In addition, 6 mg each of catechol-3,5-disulfonate disodium was added to the second, fourth and sixth layers.
/ M ² , 6 mg / m ² , and 18 mg / m ² . To prevent irradiation, the following dyes were added to the emulsion layer.

[0169]

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(Layer Structure) Each layer structure of the sample (001) is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ; content: 16% by mass, Zn
O; content: 4% by mass) and 8/2 of a fluorescent whitening agent (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl) stilbene.
Mixture: 0.05% by mass), including bluish dye (ultramarine)

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having an average grain size of 0.60 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 .08 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large emulsion B having an average grain size of 0.45 μm and small emulsion B having a diameter of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color mixture inhibitor (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd) -8) 0.02 Color image stabilizer (Cpd-9) 0.03 Image stabilizer (Cpd-10) 0.01 Color Image Stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture preventing layer) Gelatin 0.71 Color mixture inhibitor (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large emulsion C having an average grain size of 0.50 μm and small emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.03 Color image stabilizer (Cpd-6) 05 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.03 colors Image stabilizer (Cpd-16) 0.05 Color image stabilizer (Cpd-1) 7) 0.05 Color image stabilizer (Cpd-19) 0.06 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv-9) 0.10

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25

Seventh layer (protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol 0.04 (degree of modification 17%) Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0179]

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[0180]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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Further, the sample (00
A sample (002 ′) was prepared in which the composition of the fifth layer was changed as follows from 1).

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-sized emulsion C having an average grain size of 0.50 μm and small-sized emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 UV absorber (UV-1) 0.14 UV absorber (UV-2) 0.05 UV absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer Agent (Cpd-12) 0.02 Solvent (Solv-6) 0.23

A sample (001) was prepared in the same manner as in Preparation of Sample (001) except that the cyan coupler (ExC-2) of the emulsified dispersion C for the fifth layer was replaced with another coupler in the same molar amount according to Table 3. The emulsified dispersion prepared in the above was prepared to prepare comparative samples (002) to (003). Sample (0
01), instead of the cyan coupler (ExC-2) of the fifth layer emulsified dispersion C, the molar amount was changed to another coupler according to Table 3 according to Table 3, and the general formula (I) )), And an emulsified dispersion prepared in the same manner except that the compound represented by
To (008) and samples (101) to (115) of the present invention. The average particle size of each of the cyan coupler-containing lipophilic fine particle dispersions prepared above was 0.13.
〜0.17 μm.

The sample (001) was stored at 25 ° C. and 55% RH for 10 days, processed into a roll having a width of 127 mm, and subjected to imagewise exposure using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. Continuous processing (running test) was performed until the capacity of the color developing tank was doubled in the process. Processing process Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45ml Bleaching and fixing 38.0 ° C 45 seconds 35ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photosensitive material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. (3) The rinsing liquid is taken out of the rinsing (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (The rinsing was of the tank countercurrent type from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethyl polysiloxane surfactant 0.1 g 0.1 g (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Triethanolamine 11.6 g 11.6 g Acetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-Potassium bromide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence enhancement Whitening agent 2.5 g 5.0 g (Hakkol FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 4.5 g 5.9 g Diethylhydroxyl Amine 2.5 g 3.2 g N-ethyl-N- (β- Tansulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Water was added and 1000 ml 1000 ml pH ( 25.degree. C./adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 ml 800 ml Iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxymethylbenzenesulfinic acid 8 0.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107 ml 214 ml ammonium sulfite 16.0 g 32.0 g potassium metabisulfite 23.1 g 46.2 g Add water 1000ml 1000ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity: 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Next, each sample was subjected to gradation exposure with a three-color separation optical wedge for sensitometry using a sensitometer (Fuji Photo Film Co., Ltd., FWH type, color temperature of light source: 3200 ° K). The exposure at this time is 25 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount was 0 lx · sec (lux · sec). Each of the exposed samples is developed using the above-described processing solution in the above-mentioned processing step.
Magenta and cyan color samples were obtained.

The following evaluation was performed on the samples that developed each gradation. Table 3 shows the results. (Evaluation of processing color mixture) The magenta color-developed part was X-write 3
Using a 50 densitometer (manufactured by The X-rite Company), a cyan density C (M2.0) at a magenta density of 2.0 was determined. The smaller the value of C (M2.0), the smaller the amount of cyan color (process color mixture) during magenta color development.

(Evaluation of processing dependence) Cyan photographic sensitivity (S
0.5) and the absolute value ΔS (0.5) of the difference between the cyan photographic sensitivity (S′0.5) after the running process. The smaller the value of ΔS (0.5) shown in Table 3, the smaller the processing variation. Here, S0.5 (S'0.
5) represents the sensitivity, which was determined from the logarithm of the exposure amount giving a cyan density of 0.5.

(Evaluation of light fastness) Xenon light (100,000 lux xenon light irradiator) was applied to the sample having the cyan dye image through a UV cut filter having a light transmittance of 50% at 370 nm and a heat ray cut filter. For 15 days. The density after the light irradiation at a cyan density of 2.0 before the light irradiation was measured, and the light fastness was represented by the residual density (%).

[0200]

[Table 3]

[0201]

[Of 60]

The results shown in Table 1 show that the sample of the present invention in which the coupler represented by the general formula (CP) and the compound represented by the general formula (I) (color-mixing inhibitor) were used in combination, showed that the cyan color mixture at the time of magenta color development was obtained. Is improved, the processing fluctuation of the photographic gradation is small, and the light fastness is also excellent. On the other hand, in the comparative sample, all of the samples (101) to (103) had inferior color mixture, and the sample (1) using the comparative compound (a)
In each of Samples Nos. 04) to (106), deterioration of light fastness was observed, and samples (10) using comparative compounds (b) and (c)
7) In (108), an increase in photographic gradation variation was observed. When the color development and color reproducibility were evaluated for each of the above samples, all of the samples of the present invention showed a sufficient color development density with a maximum color density (Dmax) of 2 or more. Further, from a sensory evaluation by visual observation, a sample in which the coupler represented by the general formula (CP) and the compound represented by the general formula (I) (color mixture inhibitor) were used in combination showed less magenta or yellow turbidity in cyan. A comparative sample (0) having a highly saturated cyan color and using only a conventional cyan coupler.
02 ′) was confirmed to be a better cyan color.

That is, it is found that excellent cyan hue can be obtained without impairing the processing dependency and light fastness, and further excellent color reproducibility can be obtained by improving the magenta saturation by reducing the color mixture of the processing.

[0204]

As described above, according to the present invention, the coloring property is excellent,
It is possible to provide a silver halide color photographic light-sensitive material excellent in hue with little color mixing and good color reproducibility. Further, it is possible to provide a silver halide color photographic light-sensitive material having a color image having high stability against light, heat, air, chemicals and the like. Further, it is possible to provide a silver halide color photographic light-sensitive material having improved color development and development processing stability of a pyrrolotriazole coupler.

Claims (2)

[Claims] 1. A method according to claim 1, wherein at least one layer on the support contains at least one kind of coupler represented by the following general formula (CP) and at least one compound represented by the following general formula (I). Silver halide color photographic light-sensitive material. Embedded image (In the general formula (CP), each Z ^a and Z ^b -C
(R ³ ) = or -N =. However, one of Z ^a, Z ^b, is -N =, 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 Hammett's substituent constant σ _p values of R ¹ and R ² is 0.65 or more. is there. R ³
Represents a hydrogen atom or a substituent. X represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form 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 form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. (In the general formula (I), R ^{21 to} R ²⁸ may be the same or different and each represents a hydrogen atom or a substituent. R ²⁰ and R ²⁹ each represent a hydrogen atom, an aliphatic group,
Represents an acyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. R ³⁰ represents an aliphatic oxy group, an aryloxy group, an aliphatic amino group, or an arylamino group. R
The group of ^{20 to} R ³⁰ may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher multimer or a polymer chain. ) 2. The silver halide color according to claim 1, wherein at least one of the couplers represented by the general formula (CP) is a coupler represented by the following general formula (CP-I). Photosensitive material. Embedded image (In the general formula (CP-I), R ¹¹ , R ¹² , R ¹³ , R
¹⁴ and R ¹⁵ may be the same or different and each represent a hydrogen atom or a substituent; Z represents a group of nonmetallic atoms necessary for forming a ring structure together with carbon atoms at both ends; May be substituted with a substituent.
X ² represents a hydrogen atom or a substituent. R ¹⁶ represents a hydrogen atom or a substituent. )