JP2879498B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent color reproducibility, improved pressure resistance, and improved processing liquid fluctuation resistance. It is about.

[0002]

2. Description of the Related Art In recent years, silver chlorobromide emulsions having a very high silver chloride content have been put to practical use in order to meet the demand for rapid processing performance improvement on color photographic paper.
As disclosed in U.S. Patent No. 837, a dramatic improvement in development speed has been achieved. The degree to which color prints made using color photographic paper photosensitive materials can reproduce colors faithfully to the original subject depends not only on the performance of color negatives, but also on silver halide color photographic Needless to say, it greatly depends on the performance of the material. For this reason, research on silver halide color photographic light-sensitive materials for printing excellent in color reproduction has been conducted from various viewpoints. The ability of the resulting color print to reproduce a wide range of colors is limited by the absorption characteristics of the yellow, magenta, and cyan dyes used. If the dye's light absorption profile is broad or undesired side absorption, color turbidity occurs.

Of these, a phenol or naphthol cyan coupler is generally used to form a cyan dye image. However, since these couplers have unfavorable absorption in the green light region and the blue light region, they have a serious problem that the color reproducibility of blue and green is remarkably deteriorated. Things are strongly desired. As a means for solving this problem, a 2,4-diphenylimidazole cyan coupler described in EP 249,453 A2 has been proposed. Dyes formed from these couplers have reduced undesired absorption in the green and blue regions compared to conventional dyes, and are certainly preferred in color reproduction. However, even with these couplers, color reproducibility may not always be sufficient, and further improvement is desired. Further, these couplers have a serious problem that the reactivity with the oxidized developing agent, that is, the coupling activity is low, and the fastness of the formed dye to heat and light is extremely low, so that they can be put to practical use. Not in.

Further, although pyrazoloazole-based cyan couplers described in JP-A-64-553 and the like have reduced undesired absorption in the green and blue regions as compared with conventional dyes, they also have a problem. Color reproduction is not enough,
In addition, there is a problem that the coloring property is extremely low. In addition to excellent color reproducibility as a performance required for a color photographic paper photosensitive material, it is also important to have excellent handleability and performance stability in a color developing station. In other words, even if the color turbidity is reduced by using a coupler having a sharp light absorption profile of the dye and having less undesirable side absorption, the photosensitive material must be excellent in handleability and stability in a color developing laboratory. High image quality will be lost. As handleability, for example, fog and desensitization do not occur when pressure is applied to the photosensitive material during exposure processing, and as stability, sensitivity and gradation do not change with fluctuations in the composition of the processing solution. Are required.

[0005]

SUMMARY OF THE INVENTION The present inventors have continued to study photosensitive materials for color photographic paper having excellent color reproducibility. As a result, a pyrroloazole nucleus having a specific substituent as described below is obtained. With a cyan dye-forming coupler having
It has been found that a cyan-colored image having a sharp light absorption profile and little side absorption is obtained, and a dramatic improvement in color reproducibility is achieved. However, the light-sensitive material using the cyan dye-forming coupler causes deterioration of pressure resistance, especially sensitization due to pressure, and further deterioration of fluctuation resistance of processing factors, particularly, increase in low-density gradation change in continuous processing. This was a major problem in practical use.
Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color reproducibility, and further improved in pressure resistance and fluctuation resistance of a processing solution.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion layer containing at least a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a yellow dye formation on a support. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a coupler, the silver halide emulsion layer containing the cyan dye-forming coupler contains at least one of the cyan dye-forming couplers represented by formula (Ia). A silver chloride content of at least one kind in the grains and at least one kind selected from metal complexes of Fe, Ru, Re, Os or Ir;
This was achieved by a silver halide color photographic light-sensitive material characterized by containing 0 mol% or more of silver halide grains.

[0007]

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[0008] (In the general formula (Ia), Za is -NH- or -CH _{(R 3)} - represents, Zb and Zc each -C _(R 4) = or .R ₁ representing the -N = , R ₂ and R ₃ each have a Hammett's substituent constant σ _p value of 0.2
Represents 0 or more electron-withdrawing groups. However, the sum of the σ _p values of R ₁ and R ₂ is 0.65 or more. R ₄ represents a substituent . However, when two R ₄ are present in the formula, they may be the same or different. X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. )

The cyan dye-forming coupler represented by the general formula (Ia) of the present invention can provide a cyan color having a sharp light absorption profile and a small amount of side absorption, thereby achieving a remarkable improvement in color reproducibility. However, as described above, the light-sensitive material using the cyan dye-forming coupler has deteriorated pressure resistance, especially increased sensitization due to pressure, and further deteriorated fluctuation resistance of processing factors, and particularly, gradation of low density part in continuous processing. The change may be increased, which is a serious problem in practical use. The problem is Fe, Ru, Re,
At least one selected from metal complexes of Os or Ir
Significant improvement is achieved by using silver halide grains containing seeds in the grains and having a silver chloride content of 90 mol% or more.

JP-A-2-20853 discloses at least 4
It is disclosed that high sensitivity can be achieved by doping a high silver chloride emulsion grain with a hexacoordination complex of Re, Ru or Os having two cyan ligands. JP-A-1-105940 discloses that high silver chloride emulsion grains having a silver bromide-rich region selectively doped with iridium have excellent reciprocity characteristics without impairing the latent image stability for several hours after exposure. It is disclosed that an emulsion is obtained. Japanese Patent Application Laid-Open No. 3-132647 discloses that a high silver chloride emulsion containing iron ions has a high sensitivity, a high contrast, a small change in sensitivity to changes in illuminance and temperature during exposure, and a reduction in desensitization under pressure. Is disclosed. JP-A-4-
JP-A-9034 and JP-A-4-9035 disclose that a high silver chloride emulsion containing a specific metal complex having at least two cyanide ligands has high sensitivity, low reciprocity failure, good latent image preservability, and high pressure. It is disclosed that fog can be reduced. JP-A-62-253145 discloses that
It is disclosed that by incorporating metal ions into high silver chloride emulsion grains having a high silver bromide-containing phase, a silver halide photographic light-sensitive material suitable for rapid processing with less pressure fogging or pressure desensitization can be obtained. .

[0011] However, these prior arts do not disclose at all the variation resistance of processing factors, particularly the effect of suppressing the gradation fluctuation in the low density portion, and furthermore, the gradation change caused by a specific cyan coupler, There is no suggestion about suppression of pressure sensitization. Thus, it is surprising that the pressure resistance and the variability of processing factors produced by certain cyan couplers of this invention are significantly improved by high silver chloride emulsions containing certain metal complexes.

Hereinafter, the compound of the present invention will be described in detail. The cyan coupler represented by the general formula (Ia) of the present invention is specifically represented by the following general formulas (IIa) to (VIIIa).

[0013]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and X
Has the same meaning as in general formula (Ia). )
In the present invention, the compound represented by the general formula (IIa), (IIIa) or (IVa)
And a cyan coupler represented by the general formula (II)
Preference is given to cyan couplers represented by Ia).

The cyan coupler of the present invention has an electron-withdrawing group in which R ₁ , R ₂ and R ₃ are all 0.20 or more.
And the sum of the σ _p values of R ₁ and R ₂ is 0.65 or more. R
The sum of the σ _p values of ₁ and R ₂ is preferably 0.70 or more, and the upper limit is about 1.8.

R ₁ , R ₂ and R ₃ are each an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, a sigma _p value of 0.35 or more electron-withdrawing group, more preferably, sigma _p value of 0.60 or more electron withdrawing groups. The upper limit is an electron-withdrawing group of 1.0 or less. Hammett's rule is 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
Is an empirical rule proposed by LP Hammett
This is widely accepted today. The substituent constants determined by Hammett's rule include σ _p values and σ _m values, and these values are described in many general books.
For example, JA Dean ed. "Lange's Hand book of Chemis
try ", 12th edition, 1979 (Mc Graw-Hill) and" Chemical Area Special Issue ", No. 122, pp. 96-103, 1979
Know more about the year (Nankodo). In the present invention, R ₁ , R ₂ and R ₃ are defined by Hammett's substituent constant σ _p value, but are not limited to only those substituents having known values in the literature described in these books. Even if the value is unknown in the literature, it is, of course, included as long as it is within the range when measured based on the Hammett's rule.

Specific examples of the electron-withdrawing groups R ₁ , R ₂ and R _{3 having} a σ _p value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Cyano group, nitro group, dialkylphosphono group, dialphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocynate group Carbonyl group, halogenated alkyl group, halogenated alkoxy group,
A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, a heterocyclic group,
Examples thereof include a halogen atom, an azo group, and a selenocyanate group. Further groups which may have a substituent among these substituents may further have a substituent such as those mentioned in R ₄ to be described later.

The R ₁ , R ₂ and R ₃ are described in more detail. As the electron-withdrawing group having a σ _p value of 0.20 or more, an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4- Dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, 2-
Decyl-hexyloxycarbonylmethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl, 2,5-amylphenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (Eg, diphenylphosphono), diarylphosphinyl group (eg, diphenylphosphinyl), alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), alkyl A sulfonyl group (eg, methanesulfonyl, octanesulfonyl),
Arylsulfonyl group (for example, 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 (for example,
Methylthiocarbonyl, phenylthiocarbonyl), alkyl halide groups (eg, trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogen Alkylamino group (eg, N, N-di- (trifluoromethyl) amino), halogenated alkylthio group (eg, difluoromethylthio, 1,1,2,2-tetrafluoroethylthio), and the σ _p value An aryl group (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) or a heterocyclic group (e.g., 2-benzoxa) Zolyl, 2-benzothiazolyl, 1-phenyl-2-
Benzimidazolyl, 5-chloro-1-tetrazolyl,
1-pyrrolyl), a halogen atom (for example, a chlorine atom or a bromine atom), an azo group (for example, phenylazo) or a selenocyanate group.

Typical σ _p values of the electron-withdrawing group include a cyano group (0.66), a nitro group (0.78), a trifluoromethyl group (0.54), and an acetyl group (0. 5
0), trifluoromethanesulfonyl (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred as R ₁ , R ₂ and R ₃ are an acyl group, an acyloxy group, a carbamoyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, Examples include a halogenated aryloxy group, a halogenated aryl group, an aryl group substituted with two or more nitro groups, and a heterocyclic group. More preferably,
An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group.
More preferably, a cyano group, an alkoxycarbonyl group,
Aryloxycarbonyl and alkyl halide groups.

Particularly preferably, an alkoxycarbonyl group substituted by a cyano group, a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, or an alkoxycarbonyl group having a linear, branched or ether bond, an unsubstituted or an alkyl group or an alkoxy group Is an aryloxycarbonyl group substituted with As a combination of R ₁ and R ₂ , R ₁ is preferably a cyano group and R ₂ is a fluorine atom, an alkoxycarbonyl group substituted with an alkoxycarbonyl group or a carbamoyl group, or a straight chain,
An alkoxycarbonyl group having a branched chain or an ether bond, an unsubstituted or aryloxycarbonyl group substituted with an alkyl group or an alkoxy group.

R ₄ represents a substituent (including an atom);
As the substituent, a halogen atom, an aliphatic group, an aryl group,
Heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylaryl or heterocyclic thio group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, Ureido group, sulfamoylamino group, alkenyloxy group, formyl group, alkyl aryl or heterocyclic acyl group, alkyl aryl or heterocyclic sulfonyl group, alkyl aryl or heterocyclic sulfinyl group, alkyl aryl or heterocyclic oxy Carbonyl group, alkyl aryl or heterocyclic oxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, phosphonyl group, sulfamide group, imide group, azolyl group, hydroxy group, cyano group, Rubokishi group, a nitro group, a sulfo group, and an unsubstituted amino group or the like. Alkyl groups contained in these groups, an aryl group or heterocyclic group may be further substituted with the substituents exemplified in R _4.

More specifically, R ₄ is a halogen atom (eg, a chlorine atom or a bromine atom), an aliphatic group (eg, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group). Groups, cycloalkyl groups and cycloalkenyl groups, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 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), an aryl group (preferably having 6 to 36 carbon atoms, for example, phenyl, naphthyl, 4-hexadecoxyphenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl, 3- (2,4-ter
t-amylphenoxyacetamide) phenyl), a heterocyclic group (eg, 3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group (eg, methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy,
2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-te
rt-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), heterocyclic oxy Group (eg, 2-benzimidazolyloxy, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), alkyl / aryl or heterocyclic thio group (eg, methyl

Ruthio, ethylthio, octylthio, tetradodecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-
tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,4-triazole-
6-thio, 2-pyridylthio), acyloxy groups (eg, acetoxy, hexadecanoyloxy), carbamoyloxy groups (eg, N-ethylcarbamoyloxy, N
-Phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (eg, dodecylsulfonyloxy), an acylamino group (eg, acetamido, benzamide, tetradecaneamide, 2- (2,4-tert)
-Amylphenoxyacetamide, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecaneamide, 2- (2,4-di-t
-Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (e.g., methylamino, butylamino,
Dodecylamino, dimethylamino, diethylamino, methylbutylamino), arylamino groups (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidanilino, N-acetylanilino, 2-
Chloro-5- [α-2-tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino, 2-chloro-
5-dodecyloxycarbonylanilino), a ureido group (eg, methylureide, phenylureido, N, N-
Dibutylureido, dimethylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkenyloxy group (eg, 2-propenyloxy), formyl group , An alkyl aryl or a heterocyclic acyl group (eg, acetyl, benzoyl, 2,4-di-
tert-amylphenylacetyl, 3-phenylpropanoyl, 4-dodecyloxybenzoyl), alkyl / aryl or heterocyclic sulfonyl groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl groups (eg, octanesulfinyl, dodecyl) Sulfinyl, dodecanesulfinyl, dodecanesulfinyl, phenylsulfinyl, 3-pentadecylphenyl

Sulfinyl, 3-phenoxypropylsulfinyl), alkyl / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl,
Pentadecyloxycarbonyl), alkyl / aryl or heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino, 2,4-di-te
rt-butylphenoxycarbonylamino), a sulfonamide group (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butylbenzenesulfonamide),
A carbamoyl group (eg, N-ethylcarbamoyl, N,
N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl)
Sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), sulfamide group (eg, dipropylsulfamoylamino) ), Imide groups (eg, N-succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl groups (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy groups,
Examples include a cyano group, a carboxy group, a nitro group, a sulfo group, and an unsubstituted amino group.

R ₄ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Examples include a sulfinyl group, a phosphonyl group, an acyl group, and an azolyl group. More preferably an alkyl group, an aryl group, more preferably at least one alkoxy group, a sulfonyl group, a sulfamoyl group,
An alkyl group or an aryl group having a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent.

In the general formula (Ia), X represents a hydrogen atom or a group capable of leaving when the coupler reacts with an oxidized form of an aromatic primary amine color developing agent (hereinafter referred to as "leaving group"); When X represents a leaving group, the leaving group may be a halogen atom, an aromatic azo group, an alkyl group, an aryl group, a heterocyclic group, an alkyl group, which is bonded to the coupling position via an oxygen / nitrogen / sulfur or carbon atom. An arylsulfonyl group, an arylsulfinyl group, an alkoxyaryloxy or heterocyclic oxycarbonyl group, an alkylaryl or heterocyclic carbonyl group '' or a heterocyclic group bonded to a coupling position at a nitrogen atom in a heterocyclic ring, for example, Halogen atom, alkoxy group, aryloxy group, acyloxy group, alkyl or aryl sulfo Ruoxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl / aryl or heterocyclic thio group, carbamoylamino group, arylsulfonyl group, arylsulfonyl group, 5- or 6-membered A nitrogen-containing heterocyclic group,
There are an imide group, an arylazo group, and the like, and the alkyl group, the aryl group, or the heterocyclic group included in these leaving groups may be further substituted with a substituent for R ₄ , and two or more of these substituents In this case, the substituents may be the same or different, and these substituents may further have the substituents described for R ₄ .

The leaving group is more specifically a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonyl) Methoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), an acyloxy group ( For example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino (E.g., di-chloroacetyl amino, heptafluorobutyryl amino), alkyl or aryl sulfonamido group (e.g., methanesulfonic amino, trifluoromethanesulfonic amino, p
-Toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy),
Alkyl / aryl or heterocyclic thio group (for example,
Ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), arylsulfonyl group (eg, 2-butoxy-5-tert-octylphenylsulfonyl), arylsulfinyl group (eg, 2-butoxy-5-tert-)
Octylphenylsulfinyl), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2- Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo) and the like. Of course, these groups may be further substituted with the groups described as the substituents for R ₄ . As the leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. Desirable X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to a coupling active site with a nitrogen atom. . More preferably, it is an arylthio group.

In the cyan coupler represented by the general formula (Ia), the group represented by R ₁ , R ₂ , R ₃ , R ₄ or X is represented by the general formula (Ia)
a) containing a cyan coupler residue represented by a) to form a dimer or higher multimer, R ₁ , R ₂ , R ₃ ,
The group of R ₄ or X may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer having a high molecular chain is a typical example of an addition polymer having a cyan coupler residue represented by the general formula (Ia) homopolymer or copolymer of an ethylenically unsaturated compound. is there. In this case, the polymer may contain one or more kinds of cyan coloring repeating units having a cyan coupler residue represented by the general formula (Ia), and an acrylic acid ester, a methacrylic acid ester, or a maleic acid may be used as a copolymer component. 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 esters. Hereinafter, specific examples of the coupler of the present invention are shown, but the present invention is not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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The compounds of the present invention and their intermediates can be synthesized by known methods. For example, J. Am. Chem. Soc., 80, 5332 (1958), J. Am.
Ame. Chem., No. 81, 2452 (1959), J. Am. Chem.
Soc., 112, 2465 (1990); Org. Synth., I
270 (1941), J. Chem. Soc., 5149 (196)
2), Hetrocyclic., No. 27, 2301 (1988),
Rec. Trav. Chim., 80, 1075 (1961), the literature cited therein, or a similar method. Next, a specific synthesis example will be described. (Synthesis Example 1) Synthesis of Exemplified Compound (9) Exemplified Compound (9) was synthesized by the following route.

[0041]

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2-amino-4-cyano-3-methoxycarbonylpyrrole (1a) (66.0 g, 0.4 mol)
In a dimethylacetamide (300 ml) solution at room temperature at 3,5-dichlorobenzoyl chloride (2a) (8
3.2 g, 0.4 mol) and stir for 30 minutes. Add water and extract twice with ethyl acetate. The organic layer is collected, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and acetonitrile (300 ml)
Compound (3a) (113 g, 84
%).

A powder of potassium hydroxide (252 g, 4.5 mol) was added to a solution of (3a) (101.1 g, 0.3 mol) in dimethylformamide (200 ml) at room temperature and stirred well. Under cooling with water, hydroxylamine-o-sulfonic acid (237 g, 2.1 mol) is added little by little while taking care not to raise the temperature rapidly, and the mixture is stirred for 30 minutes after the addition. 0.1N hydrochloric acid aqueous solution is dropped, and neutralized while looking at pH test paper. Extract three times with ethyl acetate, wash the organic layer with water and saturated saline, and dry over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent, hexane: ethyl acetate = 2: 1) to obtain compound (4a) (9.50 g, 9%).

(4a) A solution of 7.04 g (20 mmol) of acetonitrile (30 ml) in carbon tetrachloride (9c
c), followed by triphenylphosphine (5.76).
g, 22 mmol) and heated under reflux for 8 hours. After cooling, water is added and extracted three times with ethyl acetate. The organic layer is washed with water and saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4: 1) to obtain (5a) (1.13 g, 17%).

1.8 g of the obtained (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane, and 1.5 g was further dissolved.
1.5 g of titanium isopropoxide was added. After keeping the reaction temperature at 110 ° C. and reacting for 1.5 hours, ethyl acetate was added and washed with water. The ethyl acetate layer was dried, distilled off, and purified by residue column chromatography to obtain 1.6 g of the desired Exemplified Compound (9). Melting point 9
7-98 ° C.

When the cyan coupler of the present invention is applied to a silver halide color light-sensitive material, it is sufficient that the support contains at least one layer containing the coupler of the present invention.
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general color light-sensitive material can be constituted by coating a support with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order. Although possible, the order may be different. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength region and a color coupler which forms a dye having a complementary color with the light to be exposed, thereby performing color reduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the color coupler may not have the above correspondence.

When the coupler of the present invention is applied to a light-sensitive material, it is particularly preferable to use it in a red-sensitive silver halide emulsion layer. The amount of the coupler of the present invention added to the light-sensitive material is generally from 1 × 10 ^-3 mol to 1 mol per mol of silver halide.
Mole, preferably 2 × 10 ^-3 mole to 5 × 10 ^-1 mole.

The silver halide emulsion grains coexisting with the cyan coupler of the present invention include Fe, Ru, Re, Os or I.
r contains a metal complex. The addition amount varies greatly depending on the type of the metal complex used, but is preferably in the range of 10 ^-3 mol to 10 ^-2 mol per mol of silver halide, and is preferably in the range of 10 ^-8 mol to 10 ^-4 mol per mol of silver halide. A range is most preferred. The metal complex used in the present invention is used for preparing silver halide grains, that is, nucleation, growth, physical ripening,
It may be added at any stage before and after chemical sensitization. Further, it may be added in several portions. These metal complexes are preferably dissolved in water or a suitable solvent before use.

The metal complex used in the present invention is particularly preferably an iridium complex. Iridium complex,
Examples of the trivalent or tetravalent iridium complex used for inclusion in the silver halide emulsion grains are shown below, but the effects of the present invention are not necessarily limited thereto. Hexachloroiridium (III) or (IV) acid salt, hexaammineiridium iridium (III) or (IV) acid salt. The addition amount of the iridium complex is preferably in the range of 10 ^-9 mol to 10 ^-4 mol per mol of silver halide, except for the iridium complex having at least two cyan ligands shown below, Most preferably, the range is from 10 ^-8 mol to 10 ^-5 mol.

The metal complex contained in the silver halide emulsion grains used in the present invention is preferably at least one selected from metal complexes of Fe, Ru, Re, Os or Ir having at least two cyanogen ligands. Used. These metal complexes are more preferably represented by the following general formula [C-1].

[0051]

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M ₁ ; Fe, Ru, Re, Os or O
s L; ligands other than CN [eg halogen (F, Cl, B
having a -2 least four cyan ligands used in the -3 or -4 _{invention; r, I), NH 3} , H 2 O, OH, OCN, SCN, N 3 ] a; 0, 1 or 2 n Specific examples of the metal complex are shown below. As counter ions of these metal complexes, ammonium and alkali metal ions such as sodium and potassium are preferably used.

[0053]

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The content of at least one selected from metal complexes having at least two cyanogen ligands used in the present invention is preferably from 10 ^-6 to 10 ^-3 mol per mol of silver halide. 5 per mole of silver
More preferably, it is from × 10 ^{−6 to} 5 × 10 ⁻⁴ mol.
In the present invention, 50% or more of the total content of at least one selected from metal complexes having at least two cyan ligands contained in silver halide grains is contained in a surface layer of 50% or less of the grain volume. It is preferred to contain.
Here, the surface layer of 50% or less of the particle volume refers to a surface portion corresponding to a volume of 50% or less of the volume of one particle. The volume of this surface layer is preferably 40% or less, more preferably 20% or less. Further, a layer not containing a metal complex may be provided further outside the surface layer containing a metal complex defined herein. To localize these metal complexes on the surface of the grains, dissolve them in water or a suitable solvent and add them directly to the reaction solution when forming the silver halide grains, or use a halogen for forming the silver halide grains. It is preferable to add them in an aqueous solution of a compound, an aqueous solution of a silver salt or another solution to form particles. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance, and deposit them on another silver halide particle, thereby containing these metal complexes.

The halogen composition of the silver halide emulsion grains coexisting with the cyan coupler of the present invention has a silver chloride content of 90%.
It must be at least mol%. Further, it is preferable that 95 mol% or more of the total silver halide constituting the silver halide grains is made of silver chlorobromide or silver chloride substantially free of silver iodide which is silver chloride. Here, "contains substantially no silver iodide" means that the silver iodide content is 1.0 mol% or less. Further preferred halogen composition of the silver halide grains is 98% of the total silver halide constituting the silver halide grains.
It is silver chlorobromide or silver chloride containing substantially no silver iodide in which at least mol% is silver chloride. The silver halide emulsion grains coexisting with the cyan coupler of the present invention preferably have a localized phase in which the silver bromide content exceeds at least 10 mol%. Such an arrangement of a localized phase having a higher content of silver bromide than that of the substrate (hereinafter referred to as a localized phase of silver bromide) is required to further exert the effects of the present invention. From the viewpoint of dependence and the like, it is necessary to be near the particle surface.
Here, “near the grain surface” means a position within 1/5 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The most preferable arrangement of the silver bromide localized phase is such that a localized phase having a silver bromide content of at least more than 10 mol% is epitaxially grown at the corners of cubic or tetradecahedral silver chloride grains.

It is preferable that the silver bromide content of such a silver bromide localized phase exceeds 10 mol%, but if the silver bromide content is too high, desensitization occurs when pressure is applied to the light-sensitive material. In some cases, characteristics unfavorable for a photographic light-sensitive material, such as a change in the composition of a processing solution, may cause a change in sensitivity or gradation. Taking these points into account, the silver bromide content of the silver bromide localized phase is determined to be 1
A range of 0 to 60 mol% is preferred, and a range of 20 to 50 mol% is most preferred. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) or the like. be able to. The localized phase of silver bromide is preferably composed of silver of 0.1 to 20% of the total silver constituting the silver halide emulsion grains coexisting with the cyan coupler of the present invention, and 0.5 to 7%. % Silver. Such an interface between the silver bromide localized phase and the other interface in the grains may have a clear phase boundary or may have a transition region in which the halogen composition changes gradually. Various methods can be used to form such a silver bromide localized phase. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Furthermore, a localized phase can also be formed by using a conversion method in which silver halide grains already formed are converted to silver halide having a lower solubility product. For example, a cube or 14
A water-soluble bromide solution is added to the tetrahedral silver halide host particles, or silver chlorobromide or silver bromide fine particles having a smaller average particle size than the silver halide host particles and a high silver bromide content are mixed. Thereafter, by ripening, a localized phase of silver bromide can be formed.

The formation of the silver bromide localized phase is preferably carried out in the presence of an iridium compound. Here, the formation of the localized phase in the presence of the iridium compound means that the iridium compound is supplied simultaneously with, immediately before, or immediately after the supply of silver or halogen for forming the localized phase. Say. For example, in the case where a silver bromide localized phase is formed by adding a water-soluble bromide solution, the solution may contain an iridium compound in advance, or another solution containing the iridium compound may be added at the same time. It is preferably performed. In the case where a silver bromide localized phase is formed by mixing silver halide fine grains having a smaller average grain size than the silver halide host grains and having a higher silver bromide content and then ripening them, silver bromide is used. It is also preferable that an iridium compound is previously contained in silver halide fine grains having a high content. The iridium compound may be present during the phase formation other than the formation of the silver bromide localized phase, but the silver bromide localized phase is preferably formed together with at least 50% of the total iridium moieties to be added. Most preferably, it is formed with at least 80% of the total iridium added.

In the present invention, the silver halide emulsion is preferably subjected to sulfur sensitization and / or gold sensitization. It is also preferable to use reduction sensitization in combination. The chemical sensitization with sulfur used in the present invention is performed using a compound containing sulfur which can react with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines). Examples of these are described in U.S. Pat. No. 1,574,9.
No. 44, No. 2,278,947, No. 2,410,
No. 689, No. 2,728,668, No. 3,65
No. 6,955. The silver halide grains of the present invention may have an outer surface having a (100) face, have a (111) face, or have both faces. Although a higher order plane may be included, a cube mainly composed of (100) planes or a tetrahedron is preferable. The size of the silver halide grains of the present invention may be within the range usually used, but preferably the average grain size is from 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size distribution representing the degree of monodispersion is preferably 0.2 or less, more preferably 0.15 or less, in terms of the ratio (s / d) between the standard deviation (s) and the average particle size (d) in statistics. preferable. It is also preferable to use a mixture of two or more monodisperse emulsions.

The light-sensitive material according to the present invention can be decolorized on a hydrophilic colloid layer by a process described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving image sharpness and the like. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, and dihydric alcohols (2 to 4) are added to the water-resistant resin layer of the support. Titanium oxide surface-treated with, for example, trimethylolethane)
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The high-boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are compounds having a melting point of not higher than 100 ° C. and immiscible with water having a melting point of not lower than 140 ° C. Any solvent can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. Alternatively, cyan, magenta or yellow couplers may be impregnated with a loadable latex polymer (eg, U.S. Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described above, or may be insoluble in water. Further, it can be dissolved in an organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 15 of U.S. Pat. No. 4,857,449.
And WO 12/723 of WO 88/00723.
The homopolymers or copolymers described on pages 30 to 30 are used, and more preferably a methacrylate-based or acrylamide-based polymer, particularly an acrylamide-based polymer, is preferable in terms of stabilizing a color image.

Further, in the photographic material according to the present invention, it is preferable to use a color image storability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, a combination with a pyrazoloazole coupler or a pyrrolotriazole coupler of the present invention is preferable. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine-based color developing agent,
For example, it is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or its oxidized product and the coupler during storage after processing.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

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

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be either low illuminance exposure or high illuminance short exposure, but for the present invention, an exposure method in which the exposure time per pixel is shorter than 10 ^-3 seconds is preferable, and a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds. Is more preferred.

Further, upon exposure, US Pat.
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional color development processing, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material As the additives for treatment and processing, those described in the following patent gazettes, in particular, EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

[Table 5]

As the cyan coupler, in addition to the cyan coupler of the present invention and the diphenylimidazole cyan coupler described in JP-A-2-33144, European Patent E
P0,333,185A2, 3-hydroxypyridine-based cyan couplers (among others, couplers obtained by giving a chlorine leaving group to a 4-equivalent coupler (42) of coupler (42) listed as specific examples), and couplers (6 ) And (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are particularly preferred.
May be used in combination.

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to upper right, page 34. The method described in the column is preferably applied.

[0075]

EXAMPLES The present invention will be described below in detail with reference to Examples, but the present invention is not limited thereto. Example 1 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 0 ° C., 3.3 g of sodium chloride was added and the temperature was raised to 70 ° C. Subsequently, a solution prepared by dissolving 100 g of silver nitrate in 400 cc of distilled water and a solution prepared by dissolving 34.4 g of sodium chloride in 400 cc of distilled water were added to and mixed with the above solution over 43 minutes while maintaining the temperature at 70 ° C. Next, silver nitrate 5
A solution obtained by dissolving 8.4 g in 200 cc of distilled water and a solution obtained by dissolving 20.1 g of sodium chloride in 200 cc of distilled water are mixed with 70
The mixture was added and mixed over 18 minutes while maintaining the temperature. After the temperature was lowered to 40 ° C., the following red-sensitive sensitizing dye E was added to silver halide 1
4 × 10 ^-5 mol per mol, then 1.6 g of silver nitrate
And potassium bromide 1.12 dissolved in 100 cc of distilled water
g was dissolved in 100 cc of distilled water and added and mixed over 8 minutes while maintaining the temperature at 40 ° C. After desalting and washing with water, 90 g of lime-processed gelatin was added, the temperature was raised to 50 ° C., and sulfur sensitization was optimally performed. The silver chlorobromide emulsion (containing 1.0 mol% of silver bromide) thus obtained was designated as Emulsion A.

A silver chlorobromide emulsion was prepared which differs from the emulsion A only in that 2.0 × 10 ^-6 mol of K ₂ IrCl ₆ was added per mol of the completed silver chlorobromide to the potassium bromide solution. ,
This was Emulsion B. Emulsion A was prepared by adding 1.0 × 10 ⁻⁵ mol of K ₃ Fe (CN) ₆ per mol of the finished silver chlorobromide to 2
A silver chlorobromide emulsion was prepared which was different only in that it was added to the sodium chloride solution to be added the second time, and this was designated as emulsion C. Emulsion C was prepared by preparing silver chlorobromide emulsions which were different from emulsion C only in that the kind and amount of the metal complex added to the sodium chloride solution to be added for the second time were changed as shown in Table 6, and these were used as emulsions D, E,
F and G.

[0077]

[Table 6]

With respect to the emulsions A to G thus prepared, the shape, grain size, and grain size distribution of the grains were determined from electron micrographs. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. Emulsions A to G all had a grain size of 0.4
The particles were cubic particles having a particle size distribution of 9 μm and a particle size distribution of 0.09. In addition, X-ray analysis of emulsions A to G showed weak diffraction at a portion corresponding to a silver bromide content of 10 mol% to 40 mol%.

After a corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. Was prepared (sample A). The coating solution was prepared as follows.

Preparation of Coating Liquid for First Layer 153.0 g of yellow coupler (ExY), 15.0 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-2)
7.5 g and 16.0 g of color image stabilizer (Cpd-3)
To 180 g of ethyl acetate and 25 g of a solvent (Solv-1)
And 25 g of a solvent (Solv-2), and the solution is dissolved in 60 cc of 10% sodium dodecylbenzenesulfonate.
10% aqueous gelatin solution containing 10 g of citric acid
The resulting mixture was emulsified and dispersed in 00 g to prepare an emulsified dispersion A. The resulting dispersion was treated with a silver chlorobromide emulsion (cubic, 3: 7 mixture of a large-size emulsion having an average grain size of 0.88 μm and a small-size emulsion having an average grain size of 0.70 μm (silver molar ratio). Are 0.08 and 0.09, respectively. Both emulsions consist of silver halide grains in which 0.3 mol% of silver bromide is locally contained on a part of the grain surface and the rest is silver chloride). Thus, a first layer coating solution was prepared.

Preparation of Coating Solution for Fifth Layer 19.1 g of cyan coupler (ExC), 10.4 g of ultraviolet absorber (UV-2), and 1 of color image stabilizer (Cpd-1)
9.1 g, color image stabilizer (Cpd-9) 8.7 g, color image stabilizer (Cpd-10) 8.7 g, color image stabilizer (Cpd-)
11) 0.58 g, color image stabilizer (Cpd-8) 0.58
g and 0.58 g of the color image stabilizer (Cpd-6), 30.8 g of ethyl acetate, 12.7 g of the solvent (Solv-6) and 0.58 g of the solvent (Solv-1) were added and dissolved. Sodium dodecylbenzene sulfonate 3
After adding to 265 cc of a 20% aqueous gelatin solution containing 7 cc, the mixture was emulsified and dispersed by an ultrasonic homogenizer. This emulsified dispersion and the above-mentioned emulsion A were mixed and dissolved to prepare a fifth layer coating solution having the following composition. Coating solutions for the second to fourth, sixth, and seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardener for each layer is 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used. Further, Cpd-14 and Cpd-1 were added to each layer.
5 was added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following were used as spectral sensitizing dyes for each layer.

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0086]

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In the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 8.5 × 10 ^-5 mol per mol of silver halide. 7.7 × 10 ^-5 , 25 × 10 ^-5
Mole was added. In addition, the blue-sensitive emulsion layer and the green-sensitive emulsion layer
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 10 per mole of silver halide.
× 10 ^-5 mol and 20 × 10 ^-5 mol were added. The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0088]

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

[0090]

[Table 10]

[0091]

[Table 11]

[0092]

[Table 12]

[0093]

[Table 13]

[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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A light-sensitive material was prepared in the same manner as in Sample A obtained above except that the silver halide emulsion and cyan coupler of the fifth layer (red-sensitive emulsion layer) and cyan coupler were replaced as shown in Table 14. These were designated as Samples B to M. The cyan coupler was replaced with ExC equimolar. When compounds 47 and 48 were used as the cyan coupler,
The coating weight of the silver halide emulsion of the fifth layer (red-sensitive emulsion layer) in terms of silver was changed to 0.12 g / m ² . In order to examine the gradation change due to the processing variation of the thus obtained 13 types of photosensitive materials, exposure was performed for 1 second through an optical wedge and a red filter.

[0103]

[Table 14]

The exposed sample was processed using a paper processing machine using the following processing steps and a liquid having a processing solution composition.
A simulation of a continuous process (running test) was performed until the color developing tank was replenished with twice the capacity. Processing process Temperature Time Replenishment amount Tank capacity Color development 35 ° C 45 seconds 161 ml 1.7 liter Bleaching and fixing 30-35 ° C 45 seconds 215 ml 1.7 liter Rinse 1 30-35 ° C 20 seconds − 1.7 liter rinse 2 30-35 ° C 20 seconds − 1.0 l rinse 3 30 to 35 ° C. 20 seconds 350 ml 1.0 liters drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (rinse was 3 tank countercurrent system to 3 → 1.)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml ethylenediamine-N, N, N-tetramethylene phosphonic acid 1.5 g 2.0 g potassium bromide) 0.015 g-triethanolamine 8.0 g 12.0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g sodium sulfite 0.1 g 0.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoallynin sulfate 5.0 g 7.0 g N, N-bis (carboxy Methyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water to 1000 ml 1000 ml pH (water (Add potassium oxide) 10.05 10.45

[Bleach-fixing solution] (The tank solution and the replenisher are the same) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium iron diaminediaminetetraacetate 5 g Ammonium bromide 40 g Add water to 1000 ml pH (25 ° C) 6.0 [Stable solution] (Tank solution and replenisher are the same) Benzoisothiazolin-3-one 0.02 g Polyvinylpyrrolidone 0.05 g Add water to 1000 ml pH ( 25 ° C) 5.40 pH (25 ° C) 5.40 [Rinse solution] (Tank solution and replenisher are the same) Ion-exchanged water (Calcium and magnesium are each 3ppm or less)

The change in the gradation of the foot due to the processing variation is caused by the difference ΔlogEs between the logarithmic value of the exposure amount required to give the cyan density of 0.2 and 0.8 at the start of the continuous printing and the cyan density of 0.2 after the continuous processing. And the difference 対 logEe of the logarithmic value of the exposure required to give 0.8 and 0.8, and the difference △ logE (= △ logEs
− △ logEe). A positive value indicates that the tone is increased by the continuous processing, and a negative value indicates that the tone is softened by the continuous processing, and it is preferable that each value is close to zero. Table 1 shows the results
The results are shown in FIG.

In order to examine the pressure characteristics of the photosensitive material, a load of 100 g was applied to an iron needle having a diameter of 0.5 mm before exposure to 60 cm / cm.
The photosensitive material was scratched at a speed of s. This was followed by a 1 second exposure through an optical wedge and a red filter to go through the processing steps. As the evaluation of the pressure property, the difference in the density of the colored cyan between the scratched portion and the non-scratched portion of the sample which had been scratched before exposure was visually observed, and the following judgment was given. 〇: No sensitization due to scratching was observed. Δ: Slight sensitization due to scratching was observed. ×: Sensitization due to scratching is clearly recognized. These results are also shown in Table 14.

As is clear from Table 14, when the cyan coupler of the present invention is used, the gradation change especially in the foot due to the continuous processing becomes large, and when the pressure is applied to the photosensitive material before the exposure, the sensitization is clearly increased. It can be seen that these can be significantly suppressed by incorporating metal ions into the high silver chloride emulsion grains used.

Example 2 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 0 ° C., 3.3 g of sodium chloride was added and the temperature was raised to 70 ° C. Subsequently, a solution prepared by dissolving 100 g of silver nitrate in 400 cc of distilled water and a solution prepared by dissolving 34.4 g of sodium chloride in 400 cc of distilled water were added to and mixed with the above solution over 43 minutes while maintaining the temperature at 70 ° C. Next, silver nitrate 6
A solution obtained by dissolving 0.0 g in 200 cc of distilled water and a solution obtained by dissolving 20.6 g of sodium chloride in 200 cc of distilled water
The mixture was added and mixed over 18 minutes while maintaining the temperature. After the temperature was lowered to 40 ° C. and desalination and washing were performed, lime-treated gelatin 9
After addition of 0 g, the temperature was raised to 50 ° C., and the red-sensitive sensitizing dye E used in Example 1 was added to 4 × 10 4
^-5 mol was added, and then a silver bromide fine grain emulsion (average grain size: 0.05 μm) was added in such an amount that the silver bromide content became 1.0 mol%. Optimum sulfur sensitization was applied. Silver chlorobromide emulsion thus obtained (containing 1.0 mol% of silver bromide)
Was used as emulsion H.

Emulsion H was prepared by preliminarily containing 1.2 × 10 ^-6 mol of K ₂ IrCl ₆ per mol of the completed silver chlorobromide in the silver bromide fine grain emulsion and further preparing the completed chloroodor. 1.0 × 10 ⁻⁵ mol of K ₃ Fe (C
N) ₆ was prepared in a silver chlorobromide emulsion which differed only in that it was added to the sodium chloride solution to be added a second time.
And A photosensitive material different from that of Sample A of Example 1 except that the composition of each layer was changed as described below was produced, and this was designated as Sample N. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [the first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion 30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-16) 0.19 Solvent (Solv-9) 0.18 Solvent (Solv-1) 0.18 Color image stabilizer ( Cpd-18) 0.06

Second Layer (Color Mixing Prevention Layer) Gelatin 0.64 Color Mixture Prevention Agent (Cpd-4) 0.10 Solvent (Solv-2) 0.16 Solvent (Solv-3) 0.08 Third Layer ( Blue-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-sized emulsion having an average grain size of 0.55 μm and small-sized emulsion having a size of 0.39 μm (Ag molar ratio), variation coefficient of grain size distribution) Are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of the grain surface in each emulsion.) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stability Agent (Cpd-8) 0.03 Color image stabilizer (Cpd-5) 0.16 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-2) 0.02 Solvent (Solv- 8) 0.40

Fourth Layer (Ultraviolet Absorbing Layer) Gelatin 1.41 Ultraviolet Absorbing Agent (UV-3) 0.47 Color Mixing Inhibitor (Cpd-4) 0.05 Solvent (Solv-10) 0.24 Fifth Layer (Red-sensitive emulsion layer) Silver chlorobromide emulsion H 0.23 Gelatin 1.04 Cyan coupler (ExC-2) 0.32 Color image stabilizer (Cpd-8) 0.03 Color image stabilizer (Cpd-17) 0.02 Color image stabilizer (UV-2) 0.18 Color image stabilizer (Cpd-18) 0.40 Color image stabilizer (UV-19) 0.05 Solvent (Solv-11) 0.14

Sixth layer (ultraviolet ray absorbing layer) Gelatin 0.48 Ultraviolet ray absorbent (UV-3) 0.16 Color mixing inhibitor (Cpd-4) 0.02 Solvent (Solv-10) 0.08 Seventh layer (Protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

A light-sensitive material different from Sample N obtained as described above except that the silver halide emulsion and cyan coupler of the fifth layer (red-sensitive emulsion layer) and cyan coupler were replaced as shown in Table 10 was prepared. And these were designated as Samples O to R. Cyan couplers C-47 and C-48 were replaced with ExC in equimolar amounts. Compounds 47 and 48 as cyan couplers
Was used, the silver equivalent coating amount of the silver halide emulsion of the fifth layer (red-sensitive emulsion layer) was changed to 0.14 g / m ² .
In the same manner as in Example 1, the gradation change and the pressure property of the four kinds of photosensitive materials thus obtained due to processing fluctuation were examined. Table 1 shows the results
It is shown in FIG.

[0120]

[Table 15]

As is clear from the results shown in Table 15, even when the composition of each layer was changed, the excellent effect of the present invention was exhibited.

Example 3 The yellow coupler ExY of the first layer (blue-sensitive emulsion layer) of Sample B of Example 1 was replaced with ExY-2 in an equimolar amount, and the first layer including the coupler was also used without changing the composition. A sample was prepared in which the coating amount of the layer was reduced to 80%, and the same evaluation as in Example 1 was performed. In this case, the same effect as in Example 1 was confirmed.

Example 4 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 0 ° C., 3.3 g of sodium chloride was added and the temperature was raised to 75 ° C. Subsequently, a solution prepared by dissolving 100 g of silver nitrate in 400 cc of distilled water and a solution prepared by dissolving 29.2 g of sodium chloride and 10.5 g of potassium bromide in 400 cc of distilled water were added to the above solution over 45 minutes while maintaining the temperature at 75 ° C. Mixed. Next, a solution prepared by dissolving 60 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 17.5 g of sodium chloride and 6.3 g of potassium bromide in 200 cc of distilled water were used.
The mixture was added and mixed for 20 minutes while maintaining the temperature. After desalting and washing with water at 40 ° C, lime-treated gelatin 90.
0 g was added. After the temperature was raised to 50 ° C., the red-sensitive sensitizing dye E used in Example 1 was mixed with 4 × 10 ⁻⁵ per mol of silver halide.
Mole addition was performed and sulfur sensitization was further optimally performed. The silver chlorobromide emulsion (containing 15 mol% of silver bromide) thus obtained was designated as Emulsion J.

Emulsion J was obtained by adding 1.0 × 10 ⁻⁵ mol of K ₃ Fe (CN) ₆ per mol of the completed silver chlorobromide to a solution of sodium chloride and potassium bromide added for the second time. A silver chlorobromide emulsion differing only by the above was prepared, and this was designated as emulsion K.

The sample A in Example 1 was prepared by mixing the silver halide emulsion and the cyan coupler of the fifth layer (red-sensitive emulsion layer) in Table 1.
Light-sensitive materials differing only by replacement as in No. 6 were produced, and these were designated as Samples SV. Cyan coupler 48 was replaced by an equimolar amount to ExC. When Compound 48 was used as the cyan coupler, the silver equivalent coating amount of the silver halide emulsion in the fifth layer (red-sensitive emulsion layer) was changed to 0.14 g / m ² . In the same manner as in Example 1, the gradation change and the pressure property of the four kinds of photosensitive materials thus obtained due to processing fluctuation were examined. Table 16 shows the results.

[0126]

[Table 16]

From the results in Table 16, it can be seen that the effect of the present invention is that silver halide emulsion J or K having a silver chloride content of 90 mol% or less.
It can be seen that it cannot be obtained with samples S to V using.

[0128]

According to the present invention, a silver halide color photographic light-sensitive material having excellent color reproducibility, and further having improved pressure resistance and process fluctuation resistance can be obtained.

Claims (3)

(57) [Claims] A silver halide emulsion layer containing at least a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler and a silver halide emulsion layer containing a yellow dye-forming coupler on a support. The silver halide emulsion layer containing the cyan dye-forming coupler has at least one cyan dye-forming coupler represented by the general formula (Ia) and Fe, Ru, Re, and Os. Alternatively, a silver halide color photographic light-sensitive material containing silver halide grains containing at least one selected from Ir metal complexes and having a silver chloride content of 90 mol% or more. Embedded image (In the general formula (Ia), Za is -NH- or -CH (R
₃ ) —, Zb and Zc each represent —C
(R ₄ ) = or -N =. R ₁ , R ₂ and R
₃ each have a Hammett's substituent constant σ _p value of 0.20
It represents the above electron-withdrawing group. Where σ of R ₁ and R ₂
The sum of the _p values is 0.65 or more. R ₄ represents a substituent . However, when two R ₄ are present in the formula,
They may be the same or different.
X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. ) 2. The silver halide color photographic material according to claim 1, wherein the metal complex is an Ir metal complex. 3. The silver halide color photographic material according to claim 1, wherein said metal complex is a metal complex having at least two cyanogen ligands.