JP2863037B2 - 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. The present invention relates to a silver halide color photographic light-sensitive material having improved sensitivity change (latent image storability) and pressure resistance due to time variation of the color.

[0002]

2. Description of the Related Art At present, commercially available silver halide photographic light-sensitive materials and image forming methods using the same are widely used in various fields. The halogen composition of silver halide emulsions used in many of these light-sensitive materials is often silver iodobromide mainly containing silver bromide for the purpose of achieving high sensitivity, particularly in the case of photographic light-sensitive materials. . Also, for products used in markets where there is a strong demand for finishing large quantities of prints in a short delivery time, such as photosensitive materials for color photographic paper, bromide containing substantially no silver iodide is required due to the need to increase the development speed. Silver or silver chlorobromide is used. 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 of color photographic paper.
No. 7, a dramatic improvement in development speed has been achieved.

[0003] The degree of faithful color reproduction of a color print prepared using a photosensitive material for color photographic paper with respect to the original subject depends not only on the performance of the color negative, but also on the silver halide for printing. Needless to say, the performance largely depends on the performance of the color photographic light-sensitive 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 has a broad light absorption profile or undesired side absorption, color turbidity will result.

[0004] Among these dye-forming couplers, pivaloylacetoanilides used as yellow dye-forming couplers generally have a slightly longer main absorption in a blue light region exhibiting a yellow hue, and the resulting hue has an orange hue. It had the drawback of taking on. When a color image is formed using such a coupler, not only is it impossible to reproduce high-purity lemon yellow, but also the color reproduction range of the green system that uses the coloring of the yellow dye is narrowed. There was a tendency that vivid fresh green etc. could not be reproduced. Examples of yellow dye-forming couplers that solve these disadvantages are described in, for example, JP-A-63-1988.
Various couplers such as those described in JP-A-123047 and JP-A-1-173499 have been proposed, but they have not been sufficiently satisfactory in terms of color hue and color developability.

[0005]

The photosensitive material for color photographic paper is required to have not only excellent color reproducibility but also excellent handleability and performance stability in a color developing station. Is equally important. 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.
For example, it is required that the photosensitive material does not cause fogging and desensitization when pressure is applied to the photosensitive material during the exposure processing, and that the raw material has good raw preservability and good latent image preservability. ing.

The present inventors have continued to study photosensitive materials for color photographic paper having excellent color reproducibility. As a result, an indoline-based yellow dye-forming coupler can produce a yellow color having a sharp light absorption profile and little side absorption. It was found that dramatic improvement in color reproducibility was achieved. However, photosensitive materials using this yellow dye-forming coupler are:
This causes deterioration of raw storage stability and latent image storage stability, and in some cases, deterioration of pressure resistance, which is a serious problem in practical use. Therefore, the object of the present invention is to
Silver halide color photography with excellent color reproducibility, improved sensitivity change of raw material after production (raw storage), change in sensitivity due to time variation from exposure to development (latent image storage) and pressure resistance Provided is a photosensitive material.

[0007]

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 material having a silver halide emulsion layer containing a coupler, the silver halide color photographic material has a coating pH of 4.0 to 6.5 and further contains the yellow dye-forming coupler. The silver halide emulsion layer comprises (1) at least one yellow dye-forming coupler represented by the following general formula (I), and (2) Fe, Ru, Re, O
silver halide emulsion grains containing at least one selected from metal complexes of s or Ir and having a silver chloride content of 90 mol% or more; and (3) at least one of a mercaptoheterocyclic compound. Achieved by silver color photographic materials.

[0008]

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In the general formula (I), X is 1 together with a nitrogen atom.
-Represents an organic residue necessary for forming indolinyl , Y represents an aromatic group or a heterocyclic group, and Z represents a group which is released by reacting the coupler represented by the general formula with an oxidized developing agent. Express.

The yellow dye-forming coupler represented by the general formula (I) of the present invention can provide a yellow 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 this yellow dye-forming coupler may cause deterioration in raw storability and latent image storability, which is a serious problem in practical use. These problems are caused by the use of silver halide emulsion grains containing at least one selected from metal complexes of Fe, Ru, Re, Os and Ir in the grains and having a silver chloride content of 90 mol% or more. It was found that setting the coating pH to 4.0 to 6.5 greatly improved the coating pH, but at the same time, caused a problem that the pressure resistance was deteriorated. The deterioration of the pressure resistance is remarkably improved by including at least one mercaptoheterocyclic compound, and a silver halide color photographic light-sensitive material excellent in color reproducibility, handleability and stability has been invented.

JP-A-2-20853 discloses at least 4
By doping a high silver chloride emulsion with a hexacoordinate complex of Re, Ru or Os having two cyan ligands,
It is disclosed that high sensitivity can be achieved. JP 1
No.-105940 provides an emulsion having excellent reciprocity characteristics without impairing latent image stability for several hours after exposure by using a high silver chloride emulsion having a silver bromide-rich region selectively doped with iridium. It is disclosed. JP-A-3-
No. 132647 discloses that a high silver chloride emulsion containing iron ions can provide high sensitivity, high contrast, low sensitivity fluctuation against illuminance and temperature fluctuation at the time of exposure, and can reduce desensitization under pressure. I have. JP-A-4-903
Nos. 4 and 4-9035 describe 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 pressure fogging. Is disclosed. Japanese Patent Application Laid-Open No. 62-253145 discloses a silver halide photographic light-sensitive material suitable for rapid processing with less pressure fogging or desensitization by incorporating a metal ion into a high silver chloride emulsion having a high silver bromide-containing phase. It is disclosed that it can be obtained.

On the other hand, it is disclosed in Japanese Patent Application Laid-Open No. 2-6 / 1990 that the rise in fog of the photosensitive material can be suppressed by adjusting the coating pH.
940 and U.S. Pat. No. 4,917,994. Further, JP-A-2-135338 and JP-A-3-1135 disclose that fog and a change in sensitivity that occur during storage of a photosensitive material can be suppressed by maintaining a coating pH at a specific value.

However, from these prior arts,
The deterioration of raw storability and latent image storability caused by specific yellow couplers is due to the simultaneous use of both the use of high silver chloride emulsion grains containing specific metal complexes and the setting of coating pH to specific values. Could not be expected to improve synergistically. Further, in the present invention, the combination of the above-mentioned elements causes deterioration of pressure resistance, and it is not expected from the prior art that this is improved by the mercaptoheterocyclic compound, and the effect of the present invention is surprising.

[0014] Couplers represented by the general formula (I) we describe in more detail below.

The heterocyclic group represented by A is 1-indolinyl .

In the general formula (I), when Y represents an aromatic group, it is a substituted or unsubstituted aromatic group having 6 or more carbon atoms, preferably 6 to 10 carbon atoms. Particularly preferred is phenyl or naphthyl.

When Y represents a heterocyclic group in the general formula (I), it is a saturated or unsaturated, substituted or unsubstituted heterocyclic group having 1 or more carbon atoms, preferably 1 to 10, particularly preferably 2 to 5, carbon atoms. is there. Preferred examples of the hetero atom are a nitrogen atom, a sulfur atom and an oxygen atom. The number of ring members is preferably a 5- to 6-membered ring, but may be other. It may be either a single ring or a condensed ring. When Y represents a heterocyclic group, specifically, for example, 2-pyridyl, 4-
Pyrimidinyl, 5-pyrazolyl, 8-quinolyl, 2-furyl or 2-pyrrolyl.

When the group represented by A and the group represented by Y in the general formula (I) each have a substituent, examples of the substituent include a halogen atom (for example, a fluorine atom and a chloro atom) and an alkoxycarbonyl group ( 2 to 30, preferably 2 to 20 carbon atoms, for example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl), acylamino group (2 to 30 carbon atoms, preferably 2
~ 20. For example, acetamide, tetradecaneamide, 2
-(2,4-di-t-amylphenoxy) butanamide, benzamide), a sulfonamide group (having 1 to 3 carbon atoms)
0, preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide, benzenesulfonamide), carbamoyl group (2 to 30, preferably 2 to 20 carbon atoms; for example, N-butylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (C 1-30, preferably 1-20.
For example, N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3-
(2,4-di-t-amylphenoxy) butylsulfamoyl), an alkoxy group (1 to 30, preferably 1 to 20 carbon atoms, for example, methoxy, dodecyloxy), an N-acylsulfamoyl group (carbon number) 2 to 30, preferably 2
~ 20. For example, N-propanoylsulfamoyl, N-
Tetradecanoylsulfamoyl), a sulfonyl group (1 to 30, preferably 1 to 20 carbon atoms; for example, methanesulfonyl, octanesulfonyl, dodecanesulfonyl),
Alkoxycarbonylamino group (1 to 30, preferably 1 to 20 carbon atoms; for example, methoxycarbonylamino, tetradecyloxycarbonylamino), cyano group, nitro group, carboxyl group, aryloxy group (6 to carbon atoms)
20, preferably 6-10. For example, phenoxy, 4-chlorphenoxy), an alkylthio group (having 1 to 3 carbon atoms)
0, preferably 1-20. For example, methylthio, dodecylthio), ureido group (1-30 carbon atoms, preferably 1-carbon
20. For example, phenylureido), an aryl group (same as described when Y represents an aromatic group), a heterocyclic group (Y
Is the same as described when represents a heterocyclic group), a sulfo group, an alkyl group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms)
Linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted. For example, methyl, ethyl, isopropyl, cyclopropyl, trifluoromethyl, cyclopentyl, dodecyl, 2-hexyloctyl), acyl group (1 to 3 carbon atoms)
0, preferably 2-20. For example, acetyl, benzoyl), an arylthio group (C6-20, preferably 6)
-10. For example, phenylthio), a sulfamoylamino group (C0-30, preferably 0-20. For example, N
-Butylsulfamoylamino, N-dodecylsulfamoylamino), N-acylcarbamoyl group (C 2
~ 30, preferably 2-20. For example, N-dodecanoylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30, preferably 2 to 20 carbon atoms; for example, N-hexadecanesulfonylcarbamoyl, N-benzenesulfonylcarbamoyl, N- (2-octyloxy-5-ter)
t-octylbenzenesulfonyl) carbamoyl), N
-Sulfamoylcarbamoyl group (1 to 30, preferably 1 to 20 carbon atoms; for example, N- (ethylsulfamoyl) carbamoyl, N- {3- (2,4-di-t-amylphenoxy) propylsulfur Famoyl @ carbamoyl), N-sulfonylsulfamoyl group (0 to 3 carbon atoms)
0, preferably 1-20. For example, N-dodecanesulfonylsulfamoyl, N-benzenesulfonylsulfamoyl), N-carbamoylsulfamoyl group (1 carbon atom)
~ 30, preferably 1-20. For example, N- (ethylcarbamoyl) sulfamoyl, N- {3- (2,4-di-t-amylphenoxy) propylcarbamoyl} sulfamoyl), N- (N-sulfonylcarbamoyl) sulfamoyl group (1 to 30 carbon atoms) Preferably 1-2
0. For example, N- (dodecanesulfonylcarbamoyl)
Sulfamoyl, N- (2-octyloxy-5-t-
Octylbenzenesulfonylcarbamoyl) sulfamoyl), 3-sulfonyluureido group (1 to 30 carbon atoms,
Preferably 1-20. For example, 3-hexadecanesulfonyluleide, 3-benzenesulfonyluleide), 3
An acylureido group (having 2 to 30 carbon atoms, preferably 2 to 30 carbon atoms)
20. For example, 3-acetylureido, 3-benzoylureido), 3-acylsulfamide group (1 to 3 carbon atoms)
0, preferably 1-20. For example, 3-propionylsulfamide, 3- (2,4-dichlorobenzoyl) sulfamide), 3-sulfonylsulfamide group (0 carbon atoms)
~ 30, preferably 1-20. For example, 3-methanesulfonylsulfamide, 3- (2-methoxyethoxy-5-
t-octylbenzenesulfonyl) sulfamide), hydroxyl group, acyloxy group (1-30 carbon atoms, preferably 1-20. For example, propanoyloxy, tetradecanoyloxy), sulfonyloxy group (0 carbon atom)
30, preferably 0-20. Dodecanesulfonyloxy, 2-octyloxy-5-t-octylbenzenesulfonyloxy), and aryloxycarbonyl groups (7 to 20, preferably 7 to 10 carbon atoms, for example, phenoxycarbonyl).

When the group represented by A has a substituent, preferred examples of the substituent include, among those listed above,
Examples thereof include a halogen atom, an alkoxy group, an acylamino group, a carbamoyl group, an alkyl group, a sulfonamide group and a nitro group, and non-substitution is also a preferable example.

When the group represented by Y has a substituent, preferred examples of the substituent include a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, a sulfonamide group, an acylamino group, an alkoxy group, and an aryl group. Oxy group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-sulfamoylcarbamoyl group, N-sulfonylsulfamoyl group,
Examples include an N-acylsulfamoyl group, an N-carbamoylsulfamoyl group, and an N- (N-sulfonylcarbamoyl) sulfamoyl group.

The group represented by Z in the general formula (I) may be any of conventionally known coupling-off groups. Preferred Z is a nitrogen-containing heterocyclic group bonded to a coupling position with a nitrogen atom, an aromatic oxy group,
Examples include an aromatic thio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group, and a halogen atom. These leaving groups may be a photographically useful group or a precursor thereof (for example, a development inhibitor, a development accelerator, a desilvering accelerator, a fogging agent, a dye, a hardener, a coupler, an oxidized scavenger of a developing agent, a fluorescent dye, (A developing agent or an electron transfer agent) or a non-photographically useful group.

When Z represents a nitrogen-containing heterocyclic group, specifically, it is a monocyclic or condensed, substituted or unsubstituted heterocyclic group. Examples include succinimide, maleimide, phthalimide, diglycolimide, pyrrolino,
Pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl (or 4-yl), 1-tetrazolyl, indolyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, imidazolidine-2,4-dione-
3-yl (or 1-yl), oxazolidine-2,4
-Dion-3-yl, thiazolidine-2,4-dione-
3-yl, imidazolin-2-one-1-yl, oxazolin-2-one-3-yl, thiazolin-2-one-
3-yl, benzoxazolin-2-one-3-yl,
1,2,4-triazolidin-3,5-dione-4-yl, 2-pyridin-1-yl, morpholin-3,5-dione-4-yl, 1,2,3-triazol-1-yl or 2-imidazolin-5-one. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituent that the group A may have.

When Z represents a nitrogen-containing heterocyclic group, it is preferably 1-pyrazolyl, imidazolyl, 1,2,3-triazol-1-yl, benzotriazolyl, 1,2,2,3.
4-triazol-1-yl, oxazolidine-2,4
-Dione-3-yl, 1,2,4-triazolidine-
3,5-dione-4-yl or imidazolidine-
2,4-dione-3-yl. These include those having a substituent.

When Z represents an aromatic oxy group, it is preferably a substituted or unsubstituted phenoxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituent which the group represented by Y may have. Preferred substituents that the phenoxy group has, when at least one substituent is an electron-withdrawing substituent, for example, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carboxyl group, a carbamoyl group, an acyl group Or a nitro group is an example.

When Z represents an aromatic thio group, it is preferably a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituent which the group represented by Y may have. Preferred substituents of the phenylthio group include
At least one of the substituents is an alkyl group, an alkoxy group,
It is a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When Z represents a heterocyclic oxy group, the part of the heterocyclic group has the same meaning as when Y represents a heterocyclic group. When Z represents a heterocyclic thio group, a 5- or 6-membered unsaturated heterocyclic thio group is a preferred example.
For example, a tetrazolylthio group, a 1,3,4-thiadiazolylthio group, a 1,3,4-oxadiazolylthio group,
Examples thereof include a 1,3,4-triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, and a 2-pyridylthio group. When these have a substituent, examples of the substituents which may be possessed when Y represents a heterocyclic group include the substituents mentioned above. Among these, a particularly preferred substituent is an aromatic group, an alkyl group, an alkylthio group, an acylamino group, an alkoxycarbonyl group or an aryloxycarbonyl group.

When Z represents an acyloxy group, more specifically, it is an aromatic acyloxy group (7 to 11 carbon atoms, preferably a benzoyloxy group) or an aliphatic acyloxy group (2 to 20 carbon atoms, preferably 2 to 10 carbon atoms). And may have a substituent. Specific examples of the substituent include the aforementioned Y
When represents an aromatic group, the substituents which may be possessed may be mentioned. Preferred substituents are those in which at least one substituent is a halogen atom, a nitro group, an aryl group, an alkyl group or an alkoxy group.

When Z represents a carbamoyloxy group,
An aliphatic, aromatic, heterocyclic or unsubstituted carbamoyloxy group having 1 to 30, preferably 1 to 20 carbon atoms. For example, N, N-diethylcarbamoyloxy, N-
Phenylcarbamoylmorpholinocarbonyloxy, 1
-Imidazolylcarbonyloxy or N, N-dimethylcarbamoyloxy. Here, a detailed description of the alkyl group, the aromatic group and the heterocyclic group,
It is the same as defined in the description of Y.

When Z represents an alkylthio group, it is an alkylthio group having 1 to 30, preferably 1 to 20 carbon atoms. The detailed description of the alkyl group is the same as that defined in the description of Y. Preferred as the group represented by Z in the general formula (I) are a 5- to 6-membered nitrogen-containing heterocyclic group (bonded to the coupling position by a nitrogen atom), an aromatic oxy group, and a 5- to 6-membered heterocyclic ring An oxy group or a 5- to 6-membered heterocyclic thio group is exemplified.

Preferred as the group represented by Y in the general formula (I) is an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. The description of the substituent includes those described as the substituent which may be possessed when Y is an aromatic group.

In the general formula (I), the group represented by Y is
When it is a phenyl group having at least one substituent at the ortho position, the substituent at the ortho position is particularly preferably a halogen atom, an alkoxy group, an alkyl group or an aryloxy group. Among the couplers represented by the general formula (I), particularly preferred couplers are those represented by the following general formula (II)
Indicated by

[0032]

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In the formula (II), Y and Z have the same meanings as described in the formula (I), and X ₁ represents -C (R
₁ R ₂ ) represents an organic residue necessary for forming 1-indolinyl together with -N-, and R ₁ and R ₂ each represent a hydrogen atom or a substituent.

The preferred ranges and specific examples of Y and Z in the general formula (II) are the same as those described in the general formula (I). The heterocyclic group represented by B in the general formula (II) is 1-indolinyl, and examples of the substituent include those described in the description of A in the general formula (I). Also, their preferred ranges are also Ru synonymous der. Among the couplers represented by the general formula (II),
An even more preferred coupler is represented by the following general formula (III).

[0035]

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In the formula (III), R ₃ represents a hydrogen atom or a substituent, and R ₄ , R ₅ and R ₆ represent a substituent. Z represents the same meaning as described in the general formula (I),
m and n each represent an integer from 0 to 4. m, n
When each represents an integer of 2 or more, R ₄ and R ₆ may be the same or different, or may combine with each other to form a ring.

When R ₃ and R ₄ in the general formula (III) represent substituents, examples of the substituents are the same as those in the case where the group represented by A in the general formula (I) has a substituent. Is the same as Preferred examples of R ₃ are a hydrogen atom, an alkyl group, and an aryl group, and preferred examples of R ₄ include a halogen atom, an alkoxy group, an acylamino group, a carbamoyl group, an alkyl group, a sulfonamide group, and a nitro group. . m is preferably an integer of 0 to 2, particularly preferably 0 or 1.

In the general formula (III), examples of the substituent represented by R ₅ and R ₆ are the same as the examples of the substituent when the group represented by Y in the general formula (I) has a substituent. Is mentioned. R ₅ is preferably a halogen atom, an alkoxy group, an alkyl group or an aryloxy group, and a preferable example of R _{6 is} a preferable example of the substituent when the group represented by Y in the general formula (I) has a substituent. The same ones as mentioned above can be mentioned. n is preferably 0
To 2 and more preferably 1 or 2.

The couplers represented by the general formulas (I), (II) and (III) may be a dimer or a large amount thereof which is bonded to each other via a divalent or divalent or higher valent group in X, Y and Z. A body may be formed. In this case, the number of carbon atoms may be out of the specified range for each substituent. Specific examples of the coupler represented by formula (I) are shown below, but it should not be construed that the invention is limited thereto.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

[0050]

[Table 11]

[0051]

[Table 12]

[0052]

[Table 13]

[0053]

[Table 14]

[0054]

[Table 15]

[0055]

[Table 16]

[0056]

[Table 17]

[0057]

[0058]

[Table 19]

[0059]

[Table 20]

[0060]

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The compound of the present invention can be synthesized by a generally known method or a method analogous thereto. For example, it can be synthesized by the following synthesis route.

[0062]

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In the formula, X, Y and Z have the same meanings as described in formula (I). R ₁₀ represents a halogen atom (eg, a chlor atom), —OH, an alkoxy group (eg, methoxy, ethoxy), or a phenoxy group (eg, phenoxy, 4-nitrophenoxy).
Hal represents halogen. Under the reaction conditions of (a), R
_{When 10} is OH, a dehydrating condensing agent (eg, N, N
-Dicyclohexylcarbodiimide, N, N-diisopropylcarbodiimide). When R ₁₀ is a halogen atom, the reaction is performed in the presence of a dehydrohalogenating agent. Examples of the dehydrohalogenating agent include organic bases (eg, triethylamine, diisopropylethylamine,
For example, pyridine, guanidine, butoxycali, or an inorganic base (eg, sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate) is used. In the reaction from compound 3 to compound 4, a halogenating agent is used as (b). For example, bromine, chlorine, N-bromosuccinimide, N-chlorosuccinimide and the like. In the reaction of compound 4 → final product, it is common to use a dehydrohalogenating agent as (c). Examples include the organic or inorganic bases described above. In each reaction, a reaction solvent is generally used. For example,
Chlorinated solvents (eg, dichloromethylene), aromatic solvents (eg, benzene, chlorobenzene, toluene),
Amide solvents (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone), nitrile solvents (eg, acetonitrile, propionitrile), ether solvents (eg, tetrahydrofuran, ethylene glycol diethyl) ether),
Sulfone solvents (eg, dimethyl sulfone, sulfolane) or hydrocarbon solvents (eg, cyclohexane,
Normal hexane).

The synthesis can be performed by a method other than the synthesis route described above. For example, J. Org. Ch
em. , 29 , 2932 (1964). In some cases, the functional group may be further converted from 5 to lead to the final product. The change of the synthesis route or the additional reaction can be appropriately selected. Hereinafter, a specific synthesis method will be described. Other exemplified compounds can be synthesized in the same manner. Synthesis Example 1 Synthesis of Exemplified Compound (54) The compound was synthesized by the following synthesis method.

[0065]

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3.5 g of compound 6 and 1 g of compound 7
4 g was dissolved in 100 ml of N, N-dimethylformamide and 100 ml of acetonitrile. 6 g of N, N'-dicyclohexylcarbodiimide at room temperature
40 ml of an acetonitrile solution in which was dissolved was dropped. 2
After reacting for hours, the precipitated N, N'-dicyclohexylurea was separated by filtration. The solution was poured into 500 ml of water and extracted with 500 ml of ethyl acetate. The oil layer was taken using a separating funnel, washed with water, and then dried with sodium sulfate. The solvent was distilled off under reduced pressure, and hexane was added to the residue for crystallization. 1
7.2 g of compound 8 were obtained.

16 g of the compound 8 was added to dichloromethane 150
and mixed. Dichloromethane 1 containing 4.8 g of bromine
0 ml of the solution was added dropwise under ice cooling (5 ° C to 10 ° C). 10
After reacting for 1 minute, it was transferred to a separating funnel and washed with water. The oil layer (solution containing compound 9) was taken and used as it was in the next step. 8.1 g of 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine and 8.8 m of triethylamine
1 was added to 160 ml of N, N-dimethylformamide. To this solution, a dichloromethane solution of the compound 9 obtained above was added dropwise at room temperature. After reacting for 1 hour, ethyl acetate 500
Then, the mixture was added to a separating funnel and washed with water. After neutralization with dilute hydrochloric acid, the mixture was washed again with water, and an oil layer was separated. The solvent was distilled off under reduced pressure, and the residue was separated and purified by column chromatography. Silica gel was used as the filler, and ethyl acetate / hexane (1/1) was used as the eluent. The fraction containing the desired Exemplified Compound (54) was collected and the solvent was distilled off under reduced pressure to obtain 15.2 g of a wax-like Exemplified Compound (54). Synthesis Example 2. Synthesis of Exemplified Compound (2) The compound was synthesized in the same manner as in Synthesis Example 1. However, an equimolar amount of the following compound 10 was used in place of the compound 7.

[0068]

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The final product was purified by column chromatography, and 18.3 g of wax-like exemplified compound (2) was obtained.
Obtained.

The amount of the coupler represented by formula (I) of the present invention in the light-sensitive material is preferably 1 to 1 mol per mol of silver halide.
× 10 ^-3 mol to 1 mol, preferably 2 × 10 ^-3 mol to 5 mol
× 10 ^-1 mol. The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and emulsified and dispersed in an aqueous gelatin solution to form a silver halide emulsion. The added oil-in-water dispersion method is preferred. Examples of high boiling organic solvents preferably used in the oil-in-water dispersion method are described in US Pat.
No. 2,027. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application No. (OLS) 2,541,274
No. 2,541,230, JP-B-53-41091
And European Patent Publication (EP) No. 029,104, and the dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO 88/0072.
No. 3 and can be preferably used in the present invention. When emulsifying and dispersing, it is preferable to use the compounds described on pages 21 to 71 of EP 0,435,179 A2. The high boiling organic solvent can be used in a weight ratio of generally 0 to 6.0 times, preferably 0 to 4.0 times, based on the coupler.

The silver halide emulsion grains of the present invention contain F
It contains a metal complex of e, Ru, Re, Os or Ir. The amount of addition varies greatly depending on the type of the metal complex used, but is from 10 ^-9 mol to 10 ^-2 per mol of silver halide.
Is preferably in the range of 10 moles per mole of silver halide.
Most preferred is a range of ^-8 to 10 ^-4 moles. The metal complex used in the present invention may be added at any stage before preparation of silver halide grains, that is, before and after nucleation, growth, physical ripening, and 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 to be contained 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) complex salt, hexaamine iridium (III) or (IV) complex 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 to 10 ^-5 mole per mole.

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 and Ir having at least two cyanogen ligands. Used. These metal complexes are preferably represented by the following general formula [C-I].

[0074]

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In the formula [CI], M ₁ is Fe, Ru, R
e, Os or Ir, L is a ligand other than CN, a
Represents 0, 1 or 2, and n represents -2, -3 or -4. Specific examples of the metal complex having at least two cyan ligands used in the present invention are shown below. As counter ions for these metal complexes, ammonium and sodium,
An alkali metal ion such as potassium is preferably used.

[0076]

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The content of at least one selected from metal complexes of Fe, Ru, Re, Os and Ir having at least two cyanogen ligands used in the present invention is at least 10 ^-6 mol per mol of silver halide, And preferably not more than 10 ^-3 mol, more preferably not more than 5 mol per mol of silver halide.
More preferably, it is at least ^10-6 mol and not more than 5 ^10-4 mol. The metal complex having at least two cyanogen ligands used in the present invention may be added and contained at any stage before the preparation of silver halide grains, that is, before and after nucleation, growth, physical ripening, and chemical sensitization. Further, it may be added and contained by dividing it several times. In the present invention, the total content of the metal complex having at least two cyanogen ligands contained in the silver halide grains is 50%.
% Or more in the surface layer of 50% or less of the particle volume. 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. Also,
A layer not containing a metal complex may be provided further outside the surface layer containing a metal complex as defined herein. These metal complexes are dissolved in water or a suitable solvent and added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, in an aqueous silver salt solution, Alternatively, it is preferable to add it to the solution by adding it to a solution to form particles. Further, it is also preferable to add and dissolve silver halide fine particles containing a metal complex in advance and to deposit on a separate silver halide particle to contain these metal complexes.

The halogen composition of the silver halide emulsion grains of the present invention must have a silver chloride content of 90 mol% or more. Further, it is preferable that 95 mol% or more of the total silver halide constituting the silver halide grains is silver chloride which is 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. A more preferred halogen composition of the silver halide grains is silver chlorobromide or silver chloride containing substantially no silver iodide, wherein 98 mol% or more of the total silver halide constituting the silver halide grains is silver chloride. . The silver halide grains of the present invention have a silver bromide content of at least 1
It is preferable to have a localized phase exceeding 0 mol%. Such an arrangement of the localized phase having a silver bromide content higher than that of the substrate is in the vicinity of the particle surface in order to exhibit the effects of the present invention, and further from the viewpoints of pressure properties, processing solution composition dependency, and the like. Is preferred. 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 preferred arrangement of the localized phase having a higher content of silver bromide than the substrate is that a localized phase having a silver bromide content of at least 10 mol% or more is epitaxially grown at corners of cubic or tetradecahedral silver chloride grains. It is.

The silver bromide content of such a localized phase is preferably more than 10 mol%, but if the silver bromide content is too high, desensitization may occur when pressure is applied to the light-sensitive material. In some cases, characteristics unfavorable for photographic light-sensitive materials, such as a large change in sensitivity and gradation due to a change in the composition of the processing solution, may be provided. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is preferably in the range of 10 to 70 mol%, and 20 to 50 mol%.
A mole% range is most preferred. The silver bromide content of the localized phase having a high silver bromide content can be determined by an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) and the like. Can be used to analyze. The localized phase is preferably composed of silver in an amount of 0.1 to 20 mol% of the total silver constituting the silver halide grains of the present invention, and is preferably composed of silver in an amount of 0.5 to 7 mol%. More preferably, it is performed. The interface between such a localized phase and another phase 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 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. Further, a localized phase can be formed by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. For example, a water-soluble bromide solution is added to cubic or tetradecahedral silver halide host grains, or silver chlorobromide or bromide having a smaller average grain size than the silver halide host grains and a higher silver bromide content. After mixing silver halide fine particles and aging, a localized phase can be formed.

The formation of such a localized phase is preferably performed 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, when a localized phase is formed by adding a water-soluble bromide solution, it is preferable to previously add an iridium compound to the solution or to simultaneously add another solution containing the iridium compound. . When a localized phase is formed by mixing silver halide fine grains having a smaller average grain size than silver halide host grains and having a high silver bromide content and then ripening, the silver bromide content is high. It is also preferable to incorporate an iridium compound in the silver halide fine grains in advance. An iridium compound may be present during the phase formation other than the formation of such a localized phase, but the localized phase is preferably formed together with at least 50 mol% of the total iridium to be added. Most preferably, it is formed with at least 80 mol% 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, 2,278,947, 2,410,68
No. 9, 2,728,668, 3,656,955
No. etc. The silver halide grains of the present invention,
Even if the outer surface has a (100) plane, (11)
1) It may have a plane, or both, or may include a higher-order plane. However, a cube mainly composed of a (100) plane, Alternatively, a tetrahedron is preferred. 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 the ratio (s / d) between the standard deviation (s) and the average particle size (d) in statistics. . It is also preferable to use a mixture of two or more monodisperse emulsions.

The coating pH of the silver halide color photographic light-sensitive material in the present invention is the pH of all the photographic constituent layers obtained by coating a coating solution on a support, and does not always coincide with the pH of the coating solution. do not do. The coating pH can be measured by the following method as described in JP-A-61-245153. That is, (1) 0.05 cc of pure water is dropped on the surface of the photosensitive material on which the silver halide emulsion is coated. Next, (2) After standing for 3 minutes, the coating pH is measured with a coating pH measuring electrode (TOA GS-165F). The light-sensitive material of the present invention has a coating p obtained by such a measuring method.
H is 4.0 to 6.5. Preferably, 5.0 to
6.5. The coating pH can be adjusted using an acid (eg, sulfuric acid, citric acid) or an alkali (eg, sodium hydroxide, potassium hydroxide). The method of adding these acids or alkalis is not particularly limited, but it is an easy method to carry out when preparing a coating solution. The coating solution for adding an acid or an alkali is any of the photographic constituent layers,
One or more coating solutions may be used.

As the mercaptoheterocyclic compound used in the present invention, a compound represented by the following general formula (IV) is preferable. General formula (IV)

[0084]

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In the formula, Q represents a group of atoms necessary to form a 5- or 6-membered heterocyclic ring or a 5- or 6-membered heterocyclic ring to which a benzene ring is fused, and M represents a cation.

The compound of the formula (IV) will be described below in detail. Examples of the heterocyclic ring formed by Q include an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, and a naphthoselenazole. And a benzoxazole ring. Examples of the cation represented by M include a hydrogen ion, an alkali metal (eg, sodium and potassium), an ammonium group, and the like. The compound represented by the general formula (IV) is more preferably a mercapto compound represented by the following general formulas (IV-1), (IV-2), (IV-3) and (IV-4). General formula (IV-1)

[0087]

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In the formula, _RA represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z represents -NH-, -O Represents-or -S-, and M has the same meaning as M in formula (IV). General formula (IV-2)

[0089]

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In the formula, Ar is

[0091]

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R _B represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group,
Represents a carbamoyl group or a sulfonamide group. n is 0
Represents an integer of ２2. M has the same meaning as M in formula (IV).

In the general formulas (IV-1) and (IV-2), examples of the alkyl group represented by R _A and R _B include methyl, ethyl and butyl, and examples of the alkoxy group include methoxy and ethoxy. Examples of the salt of a carboxyl group or a sulfo group include a sodium salt and an ammonium salt.

In formula (IV-1), the aryl group represented by _RA includes, for example, phenyl and naphthyl, and the halogen atom includes, for example, chlorine and bromine. In Formula (IV-2), examples of the acylamino group represented by R _B include methylcarbonylamino,
Examples include benzoylamino and the like. Examples of the carbamoyl group include ethylcarbamoyl and phenylcarbamoyl. Examples of the sulfonamide group include methylsulfonamide and phenylsulfonamide. The above-mentioned alkyl group, alkoxy group, aryl group, amino group, acylamino group, carbamoyl group, sulfonamide group and the like include those further having a substituent. The substituent may be, for example, an amino group substituted with an alkylcarbamoyl group, that is, an alkyl-substituted ureido group. General formula (IV-3)

[0095]

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In the formula, Z represents -N (R _A1 )-, an oxygen atom or a sulfur atom. R represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, -SR _A1 ,-
N (R _A2 ) R _A3 , —NHCOR _A4 , —NHSO ₂ R _A5 or a heterocyclic group; R _A1 represents a hydrogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, -CO
R _A4 or —SO ₂ R _A5 , R _A2 and R _A3 represent a hydrogen atom, an alkyl group, or an aryl group, and R _A4 and R _A5 represent an alkyl group or an aryl group. M has the same meaning as M in formula (IV).

In the general formula (IV-3), R, R _A1 ,
Examples of the alkyl group of R _A2 , R _A3 , R _A4 and R _A5 include methyl, benzyl, ethyl and propyl, and examples of the aryl group include phenyl and naphthyl. The alkenyl groups for R and R _A1 include, for example, propenyl, and the cycloalkyl groups include, for example, cyclohexyl. Examples of the heterocyclic group for R include furyl and pyridinyl. The above R, R _A1 , R _A2 , R
_The alkyl group and the aryl group represented by _A3 , R _A4 and R _A5 , the alkenyl group and the cycloalkyl group represented by R and R _A1 , and the heterocyclic group represented by R include those further having a substituent. General formula (IV-4)

[0098]

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In the formula, R and M are each represented by the general formula (IV-
It represents the same group as R and M in 3). R _B1 and R _B2 each represent a group having the same meaning as R _A1 and R _A2 in formula (IV-3). Hereinafter, specific examples of the compound represented by the general formula (IV) are shown, but the present invention is not limited thereto.

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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The amount of the compound represented by the general formula (IV) is from 1 × 10 ^{-5 to} 5 × 10 ^-2 per mol of silver halide.
Mol is preferable, and 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol is more preferable. The method of addition is not particularly limited, and may be during formation of silver halide grains, during physical ripening, during chemical ripening, or during preparation of a coating solution.

The light-sensitive material of the present invention contains a hydrophilic colloid layer in order to prevent irradiation and halation and to improve the safety of safe lights, etc.
No. 337,490A2, pages 27 to 76,
It is preferable to add a dye (oxonol dye, cyanine dye) that can be decolorized by the treatment. In addition, Japanese Unexamined Patent Application Publication No.
No. 282244, page 3, right upper column to page 8 and dyes described in JP-A-3-7931, page 3, upper right column to page 11, lower left column, in the form of solid fine particle dispersion, hydrophilic colloid layer. And a dye which is decolorized in the developing process by being contained in the dye. When these dyes are used, it is preferable to select and use a dye having an absorption that overlaps the spectral sensitivity of the longest-wavelength photosensitive layer.
Using these dyes, the optical density (the logarithm of the reciprocal of transmitted light) at 680 nm of the light-sensitive material or the laser wavelength used for exposure (the reflection density in the case of a reflective support) is 0.5 or more. Is preferable in order to improve sharpness. In order to further improve sharpness, the water-resistant resin layer on the support contains 12% by weight or more (more preferably 14% by weight) of titanium oxide surface-treated with a divalent or tetravalent alcohol (eg, trimethylolethane) or the like. % Or more). Further, Japanese Patent Laid-Open No. 1-23
It is also preferred to use colloidal silver for the antihalation layer as described in US Pat.

In the light-sensitive material of the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589 A2 together with a coupler. In particular, a combination with a yellow coupler, a pyrazoloazole coupler or a pyrrolotriazole coupler used in the present invention is preferable. That is, the compound (F) which chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inert and substantially colorless compound, and / or
Alternatively, a 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 remaining after color development processing is used simultaneously or independently. However, it is preferable in order to prevent, for example, 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 the oxidized product thereof and the coupler during storage after processing.

The light-sensitive material of the present invention is provided with a fungicide such as that described in JP-A-63-271247 in order 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 the support used in the light-sensitive material of the present invention, a white polyester-based support for display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used. You may. To further improve sharpness,
It is preferred to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. Further, as a support used for the photosensitive material according to the present invention, a transparent support is also preferably used. In this case, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface.

The exposed light-sensitive material can be subjected to conventional color development processing. In the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is adjusted to about 6.
It is preferably 5 or less, more preferably about 6 or less. Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material of the present invention, and processing methods and processing additions applied for processing this light-sensitive material As the agent, the following patent publications, especially European patent EP
0,355,660A2 (Japanese Unexamined Patent Publication (Kokai) No. 2-139544)
No.) those described in the specification are preferably used.

[0112]

[Table 21]

[0113]

[Table 22]

[0114]

[Table 23]

[0115]

[Table 24]

Further, as the cyan coupler, JP-A-2-
In addition to the diphenylimidazole cyan coupler described in JP-A-33144, European Patent EP 0,333,185
No. A2, 3-hydroxypyridine cyan couplers (in particular, couplers (4)
(2) 4-equivalent coupler having a chlorine leaving group to give a 2-equivalent coupler, and couplers (6) and (9) are particularly preferred)
Also, the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are preferable. Further, a conventionally known yellow coupler can be used in combination with the yellow coupler having the structure of the general formula (I) used in the present invention. Table 21 shows yellow couplers that can be used in combination. Further, a cycloalkane type yellow coupler described in European Patent EP 0,447,969 A1 can also be used in combination.

The magenta coupler used in the present invention includes 5-
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. Among them, secondary or tertiary alkyl groups such as those described in JP-A-61-65245 are particularly preferred in terms of hue, image stability, and coloring properties. Pyrazolotriazole couplers directly linked to the 2, 3 or 6-position of the pyrazolotriazole ring; pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246; Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in EP-147254;
No. 6 described in Nos. 49A and 294,785A
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the position.

The processing method of the color light-sensitive material of the present invention includes:
The method described in JP-A-2-207250 is preferred. The processing temperature of the color developer applicable to the present invention is 20 to 5
0 ° C., preferably 30 to 45 ° C. The replenishing amount is preferably small, but the replenishing amount is preferably ^{20 to} 600 m / m ^{2 of} the photosensitive material.
l is suitable, preferably 50-300 ml.
More preferably 60-200 ml, most preferably 60 ml.
１５０150 ml.

The preferable pH of the washing step or the stabilizing step is 4
-10, and more preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material.
The temperature is 0 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily, but a shorter method is desirable from the viewpoint of reducing the processing time. Preferably 10 to 45 seconds, more preferably 1
0 to 40 seconds. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability and the like. A specific preferable replenishing amount is 0.5 to 50 times, preferably 2 to 15 times the carry-in amount from the previous bath per unit area of the light-sensitive material.
It is twice. Or the light-sensitive material 1 m ² per 300ml or less,
Preferably it is 150 ml or less. Replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

[0120]

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 40 ° C., 5.76 g of sodium chloride was added and the temperature was raised to 75 ° C. Then 100g of silver nitrate
Of sodium chloride dissolved in 400 cc of distilled water and sodium chloride 3
A solution prepared by dissolving 4.4 g in 400 cc of distilled water was added at 75 ° C.
Was added to and mixed with the above solution over 73 minutes.
Next, a solution prepared by dissolving 59.2 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 17.1 g of sodium chloride in 200 cc of distilled water were added and mixed over 28 minutes while maintaining the temperature at 75 ° C. After cooling to 40 ° C., a blue-sensitive sensitizing dye A shown below
And B were added in an amount of 2 × 10 ^-4 mol per mol of silver halide, and then a solution prepared by dissolving 0.8 g of silver nitrate in 100 cc of distilled water and 0.56 g of potassium bromide in 100 cc of distilled water.
Was added and mixed over 10 minutes while maintaining 40 ° C. After desalting and water washing, 90 g of lime-processed gelatin was added, and sulfur sensitization was optimally performed. The silver chlorobromide emulsion (containing 0.5 mol% of silver bromide) thus obtained was designated as Emulsion A.

Emulsion A was prepared by adding K ₂ I in a potassium bromide solution.
rCl ₆ is added in an amount of 1.0 per mole of finished silver chlorobromide.
A silver chlorobromide emulsion (containing 0.5 mol% of silver bromide) was prepared which was different only in that it was added in an amount corresponding to × 10 ^-6 mol. Emulsion A is the same as Emulsion A except that K ₄ Fe (CN) ₆ was added to the second addition of sodium chloride solution in an amount corresponding to 8.0 × 10 ⁻⁶ mol per mol of the completed silver chlorobromide. A different silver chlorobromide emulsion (containing 0.5 mol% of silver bromide) was prepared and used as Emulsion C. Emulsion A was prepared in the same manner as emulsion A except 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 A, and these emulsions were prepared as emulsions D, E, F and G And

[0122]

[Table 25]

With respect to the emulsions A to G thus prepared, the shape, the grain size, and the grain size distribution of the grains were determined from an electron micrograph. 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 0.7
The particles were cubic particles having a particle size distribution of 0 μm and a particle size distribution of 0.09. The X-ray diffraction 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 1). The coating solution was prepared as follows.

Preparation of coating solution 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)
With ethyl acetate (180 cc) and solvent (Solv-1) 25
g) and 25 g of a solvent (Solv-2), and this solution is dissolved in 10% sodium dodecylbenzenesulfonate 60.
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% aqueous gelatin solution containing 10 g of cc and citric acid.
The obtained dispersion was mixed and dissolved with silver chlorobromide emulsion A to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-14 and Cp
d-15 in a total amount of 25.0 mg / m ² and 50.
0 mg / m ² was added. The following were used as the spectral sensitizing dyes in each layer.

[0127]

[Table 26]

[0128]

[Table 27]

[0129]

[Table 28]

In the green-sensitive emulsion layer and the blue-sensitive emulsion layer, 1-
(5-methylureidophenyl) -5-mercaptotet
Lazole was added to each of 7.7 × per mole of silver halide.
10 ^-FourMol, 2.5 × 10^-FourMole was added. Blue-sensitive emulsion
4-hydroxy-6-methyl
-1,3,3a, 7-tetrazaindene is halo
1.0 × 10 per mol of silver genide^-FourMole, 2.0 × 1
0^-FourMole was added. Also, to prevent irradiation
Add the following dyes to the emulsion layer
Added.

[0131]

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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.

[0133]

[Table 29]

[0134]

[Table 30]

[0135]

[Table 31]

[0136]

[Table 32]

The sample 1 thus obtained was replaced with the silver halide emulsion and yellow coupler of the first layer (blue-sensitive emulsion layer) as shown in Table B, and the compounds shown in Table B were replaced with the compounds shown in Table B. Photosensitive materials were prepared by adding the coating solution to the first layer and further changing the coating pH as shown in Table B, and these were designated as Samples 2 to 26. However, as a photosensitive material using a compound of the present invention is a yellow coupler, emulsion coating amount and coupler coating amount of the blue-sensitive emulsion layer in order to align the color density of each 0.19 g / m ² and 0.55 g / m ² changed.

[0138]

[Table 33]

[0139]

[Table 34]

In order to examine the change in sensitivity (latent image preservability) due to the change in the time interval from the exposure of the photosensitive material to the processing, the exposure was carried out for 1 second through an optical wedge and a blue filter, 10 minutes after exposure and 35 minutes. After 3 hours in an atmosphere of 40 ° C. and 40% RH, color development was performed using the following processing steps and processing solutions. The change in sensitivity (ΔS latent image) was represented by the difference between the logarithmic value of the exposure amount required to give a density higher than the fog density by 1.0. Positive values indicate that sensitization occurs over time after exposure.

As an evaluation of the change in photographic performance (raw storage property) due to long-term storage of the photosensitive material, a sample was prepared at 60 ° C. and 40% RH.
After storage for 2 days in the atmosphere described above, the above exposure and treatment were performed, and the change in sensitivity (ΔS raw storage) with the sample not stored in the atmosphere was measured.

In order to examine the pressure resistance of the light-sensitive material, the light-sensitive material was exposed for about 30 minutes with the coated surface of the photographic constituent layer inside before exposure.
The above exposure and processing were performed after folding at an angle of °.
As an evaluation of pressure resistance, a sample folded before exposure was visually observed, and the following judgment was given. ；: No desensitization due to folding was observed. Δ: Desensitization due to folding was slightly observed. X: Desensitization due to folding is clearly recognized. The results are shown in Table-B.

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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Processing Step Temperature Time Color development 35 ° C. 45 seconds Bleaching and fixing 30-35 ° C. 45 seconds Rinse 1 30-35 ° C. 20 seconds Rinse 2 30-35 ° C. 20 seconds Rinse 3 30-35 ° C. 20 seconds Drying 70- 80 ℃ 60 seconds

The composition of each processing solution is as follows. [Color developer] Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g N, N-di (sulfoethyl ) Hydroxylamine.1Na 4.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Add water 1000 ml pH (25 ° C.) 10.05

[Bleaching-fixing solution] Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g ml pH (25 ° C) 6.0 [Rinse solution] Deionized water (Calcium and magnesium are each 3 ppm or less)

As is clear from the results shown in Table B, the light-sensitive material containing a yellow coupler, a high silver chloride emulsion containing a metal complex and a mercaptoheterocyclic compound and having a coating pH of a specific value according to the present invention was found to be latent. Excellent image storability, raw storability and pressure resistance.

Example 2 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 40 ° C., 3.3 g of sodium chloride was added to raise the temperature to 74 ° C. Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and sodium chloride.
A solution prepared by dissolving 0 g in 200 cc of distilled water was added to and mixed with the above solution over 18 minutes while maintaining the temperature at 74 ° C. Further, a solution prepared by dissolving 128.0 g of silver oxide in 560 cc of distilled water and a solution prepared by dissolving 44.0 g of sodium chloride in 560 cc of distilled water were added and mixed over 50 minutes while maintaining 74 ° C. However, K ₄ Fe (CN) ₆ was contained in the sodium chloride solution to be added for the second time, and the resulting silver chlorobromide 1 was added.
An amount corresponding to 5.0 × 10 ^-6 mole per mole was added. After desalting and washing, 90.0 g of lime-processed gelatin was added, and the same blue-sensitive sensitizing dyes A and B as used in Example 1 were each added in an amount of 2.0 × 10 ⁻ per mol of silver halide. After the addition of ⁴ mol, the ultrafine silver bromide emulsion (particle size 0.05 μm, containing K ₂ IrCl ₆ in an amount equivalent to 1.0 × 10 ⁻⁶ mol per mol of the completed silver chlorobromide emulsion) was salted. Gold bromide sensitization was optimally performed by adding an amount containing 0.4 mol% of silver bromide to silver. The silver chlorobromide emulsion (containing 0.4 mol% of silver bromide) thus obtained was designated as Emulsion H.

32 g of lime-processed gelatin was added to distilled water 800 c
c) and dissolved at 40 ° C., and sodium chloride 3.3 was added.
g was added to raise the temperature to 74 ° C. Subsequently, a solution prepared by dissolving 32.0 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 9.35 g of sodium chloride and 3.36 g of potassium bromide in 200 cc of distilled water were mixed while maintaining 74 ° C.
The mixture was added to the above solution over 8 minutes. Further silver nitrate 12
A solution prepared by dissolving 8.0 g in 560 cc of distilled water and a solution prepared by dissolving 37.4 g of sodium chloride and 13.4 g of potassium bromide in 560 cc of distilled water were mixed at 50.degree.
The mixture was added over a period of minutes. However, in the sodium chloride solution to be added for the second time, K ₄ Fe (CN) ₆ and K ₂ IrCl ₆ were added in an amount of 5.0 × 10 ^-6 mol and 1.0 × 10 ⁶ mol, respectively, per mol of the finished silver chloride. An amount corresponding to ^-6 mol was added. After desalting and washing with water, 90.0 g of lime-processed gelatin was added, and the same blue-sensitive sensitizing dyes A and B as used in Example 1 were each added in an amount of 2.0 × 10 ⁻ per mole of silver halide. After the addition of ⁴ mol, gold-sulfur sensitization was optimally performed. The silver chlorobromide emulsion (containing 15 mol% of silver bromide) thus obtained was added to the emulsion layer I.
And

With respect to the two types of emulsions H and I thus prepared, the particle shape, particle size, and particle size distribution 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. The two types of emulsions, H and I,
In each case, the particle size was 0.71 μm, and the particle size distribution was 0.1 μm.
08 cubic particles.

A photosensitive material was prepared by changing the composition (additives and coating amounts) of the respective layers from Sample 1 obtained in Example 1 as follows, and this was designated as Sample 27. 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 side polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion H 0 .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 mixture preventing layer) Gelatin 0.64 Color mixture inhibitor (Cpd-4) 0.10 Solvent (Solv-2) 0.16 Solvent (Solv-3) 0.08 Third layer (green sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion with average grain size of 0.55 µm and small size emulsion with 0.39 µm (Ag mole ratio). Variation coefficient of grain size distribution is 0.10 and 0.08, respectively, and emulsions each containing 0.8 mol% of AgBr locally on a part of the grain surface and the remainder consisting of silver halide grains of silver chloride) 0.12 gelatin 1.28 magenta Coupler (ExM) 0.23 Color image stabilizer (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- ) 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 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-18) 0.40 Color image stabilizer (Cpd-19) 0.05 Solvent (Solv-11) 0.14

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.48 Ultraviolet Absorbing Agent (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 (Modification degree 17%) 0.17 Liquid paraffin 0.03

[0162]

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[0163]

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[0164]

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The sample 27 obtained as described above was replaced with the silver halide emulsion and yellow coupler of the first layer (blue-sensitive emulsion layer) as shown in Table C, and the compounds shown in Table C were replaced with the compounds shown in Table C. One layer is added to the coating solution, and the coating pH is
A light-sensitive material modified as shown in C was prepared, and these were used as Sample 2.
8-34. However, in the light-sensitive material using the compound of the invention as a yellow coupler, emulsion coating amount and coupler coating amount of the blue-sensitive emulsion layer in order to align the color density of each 0.21 g / m ² and 0.57 g / m ² changed. These samples were examined for latent image storability, raw storability and pressure resistance in the same manner as in Example 1. Table-Results
C.

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[Table 35]

From Table C, it was clear that the effect of the present invention could not be obtained with a silver halide emulsion having a silver chloride content of 90 mol% or less.

[0168]

According to the present invention, a silver halide color photographic material having excellent color reproducibility, improved latent image storability, raw storability and improved pressure resistance can be obtained.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/36 G03C 1/035 G03C 1/09 G03C 1/34

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 color photographic light-sensitive material having a coating pH of 4.0 to 4.0.
6.5, and the silver halide emulsion layer containing the yellow dye-forming coupler further comprises (1) at least one kind of a yellow dye-forming coupler represented by the following general formula (I):
(2) silver halide emulsion grains containing at least one selected from metal complexes of Fe, Ru, Re, Os and Ir and having a silver chloride content of 90 mol% or more; and (3) at least one of mercaptoheterocyclic compounds A silver halide color photographic light-sensitive material comprising: Embedded image In the general formula (I), X is 1-indolini together with a nitrogen atom.
Represents an organic residue required to form a Le, Y represents an aromatic group or a heterocyclic group, Z is a group of couplers represented by the general formula is disengaged reacts with oxidized developer . 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.