JP2001228591A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having good color reproducibility and excellent also in the light resistance of a dye image. SOLUTION: The silver halide color photographic sensitive material has photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and a middle layer on the base and contains a compound of formula I, e.g. formula II in the photographic constituent layers.

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, it has good color reproducibility.
In addition, the present invention relates to a silver halide color photographic light-sensitive material having excellent light resistance of a dye image.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material (hereinafter also simply referred to as "light-sensitive material") used for direct viewing, for example, a color photographic paper, a yellow coupler, a magenta or the like is usually used as a color forming agent for forming a dye image. Combinations of couplers and cyan couplers are used. These couplers are required to have basic performance such as color reproducibility, color development and storage durability of the obtained dye image.In particular, in recent years, in order to faithfully reproduce the original color of the target object, color reproduction is required. Demands for improved performance are increasing from users.

For the purpose of improving color reproducibility, Japanese Patent Application Laid-Open No.
No. 25140, No. 4-81844, Japanese Patent Application No. 8-592
No. 89 has proposed a new yellow coupler.
Similarly, for the purpose of improving color reproducibility, see JP-A-63-250.
Nos. 649, 63-250650 and 64-554 propose pyrazolotriazole type magenta couplers. Conventionally, phenol-based or naphthol-based couplers are often used as cyan image-forming couplers. However, cyan dye images obtained from these phenol-based or naphthol-based couplers have poor absorption on the short-wave side of absorption, and have unnecessary absorption in the green region, that is, irregular absorption, so that color reproducibility is insufficient. . In order to solve this problem, pyrazolotriazole type cyan couplers have been proposed in Japanese Patent Application No. 6-333366.

However, although these yellow, magenta and cyan couplers all have good color reproducibility, it has been found that image storability, especially light fastness, is not yet satisfactory.

[0005]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide color photographic material having good color reproducibility and excellent light fastness of a dye image.

[0006]

The above object of the present invention is attained by the following constitutions.

[0007] 1. On a support, there are provided photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and an intermediate layer, and at least one of the photographic constituent layers has the following composition. A silver halide color photographic material comprising at least one compound represented by formula (I).

[0008]

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In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group or a heterocyclic group, and R ² represents an alkyl group having 1 to 12 carbon atoms. And R ³ and R ⁴ each represent a group that can be substituted on a benzene ring, m represents an integer of 0 to 2, and when m is 2, a plurality of R ³ may be the same or different. n represents an integer of 0 to 5, and when n is 2 or more, a plurality of R ⁴ may be the same or different.

[0010] 2. A photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and an intermediate layer is provided on a support. It is characterized by containing at least one kind of the yellow coupler represented by the formula (II) and at least one kind of the compound represented by the formula (I) in at least one of the photographic constituent layers. Silver halide color photographic light-sensitive material.

[0011]

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In the formula, R _A represents an aliphatic group, an aromatic group or a heterocyclic group, R _B represents a hydrogen atom, a halogen atom or an alkoxy group, and R _C represents a group substitutable on a benzene ring. , P represents an integer of 0, 1 or 2, and when p is 2, a plurality of R _{C 's} may be the same or different. _XD represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

3. The support has a photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and an intermediate layer. It is characterized by containing at least one kind of the magenta coupler represented by the formula (III) and at least one kind of the compound represented by the formula (I) in at least one of the photographic constituent layers. Silver halide color photographic light-sensitive material.

[0014]

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Where R_SRepresents a hydrogen atom or a substituent,
Y represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring.
And the ring formed by Y may have a substituent.
No. X ₀Is the reaction with hydrogen atom or oxidized form of color developing agent
Represents a group capable of leaving.

4. A photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and an intermediate layer is provided on a support. Formula (IV), (V) or (VI)
Containing at least one kind of cyan coupler represented by
And a silver halide color photographic light-sensitive material characterized in that at least one of the photographic constituent layers contains at least one compound represented by the above general formula (I).

[0017]

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In the formula, R _T represents an alkyl group having 2 to 6 carbon atoms, R _U represents a ballast group, and X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

[0019]

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Wherein R _V and R _X are each a branched alkyl group,
Represents a substituted alkyl group, a substituted aryl group or a heterocyclic group,
R _W and R _Y each represent a substituent, and X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

Hereinafter, the present invention will be described in detail. First, the compound represented by formula (I) of the present invention will be described in detail.

The alkyl group represented by R ¹ in the general formula (I) includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, i-butyl,
Examples thereof include linear or branched alkyl groups such as t-butyl, amyl, t-amyl, hexyl, octyl, i-octyl, t-octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, and octadecyl.

Examples of the cycloalkyl group represented by R ¹ include groups such as cyclopropyl, cyclopentyl, cyclohexyl and cycloheptyl.

Examples of the aryl group represented by R ¹ include phenyl, naphthyl and the like.

The heterocyclic group represented by R ¹ includes, for example, 2-pyrrolyl, 2-indolyl, 2-furyl, 2-furyl
Examples include thienyl, 2-imidazolyl, 2-thiazolyl, 3-isoxazolyl, 3-pyridyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazolyl, and 2-benzothiazolyl.

Examples of the alkyl group represented by R ² include methyl, ethyl, propyl, isopropyl, butyl, i-butyl, t-butyl, isobutyl, amyl and t-butyl.
Examples include -amyl, octyl, t-octyl, decyl, dodecyl and the like, and among them, a methyl group is preferable.

The group which can be substituted on the benzene ring represented by R ³ and R ⁴ includes, for example, halogen atom, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carbonamide,
Sulfonamide, carbamoyl, sulfamoyl, alkylsulfonyl, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxysulfonyl, acyloxy, nitro, heterocycle, cyano, acyl, alkylsulfonyloxy, arylsulfonyloxy, etc. Preferably, an alkyl group is preferable.

Hereinafter, typical specific examples of the compound represented by the formula (I) are shown, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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The compound represented by the general formula (I) of the present invention is usually used in an amount of 1 × 10 ^-4 to 1 × 10 ^-8 per photographic constituent layer.
Mole, preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-7 mole.

The compound of the present invention represented by the general formula (I) may be added in any photographic constituent layer, but in the present invention, it is located far from the support with respect to each silver halide emulsion layer. It is preferably added to a certain photographic constituent layer,
In particular, it is preferably added to a photographic constituent layer between the green-sensitive emulsion layer and the red-sensitive emulsion layer and a photographic constituent layer closer to the surface than the red-sensitive emulsion layer.

The yellow coupler of the present invention represented by formula (II) will be described. In the general formula (II), examples of the aliphatic group represented by R _A include a linear, branched or cyclic alkyl group which may be substituted or contain an unsaturated bond, for example, Methyl, isopropyl, t-butyl, cyclopropyl, cyclopentyl, t
-Pentyl, cyclohexyl, 2-ethylhexyl,
1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl,
Examples include benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, and phenoxyethyl, and among them, a branched alkyl group is preferable.

As the aromatic group represented by R _A , an optionally substituted monocyclic or condensed-ring aryl group, for example, phenyl, 1-naphthyl, 9-anthranyl, p-
Tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4- Examples include di-t-pentylphenyl, p-methanesulfonamidophenyl, and 3,4-dichlorophenyl, and among them, a phenyl group and a 4-methoxyphenyl group are preferable.

The heterocyclic group represented by R _A includes O,
At least one selected from N, S, P, Se and Te
3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic groups having two or more heteroatoms in the ring, for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl,
-Imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide,
-Benzyl-2,4-imidazolidindion-3-yl and the like.

In the general formula (II), the aliphatic group, aromatic group and heterocyclic group represented by R _A may have a substituent. Examples thereof include groups each having the same meaning as the aliphatic group, aromatic group and heterocyclic group represented by R _A , and in addition, carbonyl groups (for example, alkylcarbonyl groups such as acetyl group and trifluoroacetylpivaloyl group; Benzoyl group, pentafluorobenzoyl group, 3,5-di-t-butyl-4
Arylcarbonyl groups such as -hydroxybenzoyl group, etc.), oxycarbonyl groups (e.g., alkoxycarbonyl groups such as methoxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group; phenoxycarbonyl group, 2,4-di-t-amylphenoxy) Aryloxycarbonyl groups such as carbonyl group and 1-naphthyloxycarbonyl group; heterocyclic oxycarbonyl groups such as 2-pyridyloxycarbonyl group and 1-phenylpyrazolyl-5-oxycarbonyl group; carbamoyl group (for example, dimethylcarbamoyl group) Alkylcarbamoyl groups such as, 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group; phenylcarbamoyl groups;
Arylcarbamoyl groups such as 1-naphthylcarbamoyl group, etc.), sulfonyl groups (eg, alkylsulfonyl groups such as methanesulfonyl group and trifluoromethanesulfonyl group; arylsulfonyl groups such as p-toluenesulfonyl group, etc.), and sulfamoyl groups (eg, dimethylsulfonyl group). An alkylsulfamoyl group such as a famoyl group, 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl group; an arylsulfamoyl group such as a phenylsulfamoyl group; and a halogen atom. Alkyl group (eg, trifluoromethyl group), halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, nitro group, alkenyl group (eg, 2-propylene group, oleyl group, etc.), hydroxy group, alkoxy group (eg, Methoxy group, 2-ethoxyethoxy group, etc.) An aryloxy group (e.g., phenoxy group, 2,4-di -t- amylphenoxy group, 4-
(4-hydroxyphenylsulfonyl) phenoxy group and the like), heterocyclic oxy group (for example, 4-pyridyloxy group,
2-hexahydropyranyloxy group, etc.), carbonyloxy group (for example, alkylcarbonyloxy group such as acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group, etc .; aryloxy group such as benzoyloxy group, pentafluorobenzoyloxy group, etc.) ), Urethane groups (eg, alkyl urethane groups such as N, N-dimethyl urethane group; aryl urethane groups such as N-phenyl urethane group, N- (p-cyanophenyl) urethane group, etc.), and sulfonyloxy groups (eg, methanesulfonyl) Alkylsulfonyloxy groups such as oxy group, trifluoromethanesulfonyloxy group and dodecanesulfonyloxy group; arylsulfonyloxy groups such as benzenesulfonyloxy group and p-toluenesulfonyloxy group; and amino groups (for example, dimethylamino Group, cyclohexylamino group, an alkylamino group and dodecyl amino group; anilino group, p-
an arylamino group such as a t-octylanilino group), a sulfonylamino group (for example, a methanesulfonylamino group,
Alkylsulfonylamino groups such as heptafluoropropanesulfonylamino group and hexadecylsulfonylamino group; arylsulfonylamino groups such as p-toluenesulfonyl group and pentafluorobenzenesulfonylamino; and sulfamoylamino groups (for example, N, N- Alkylsulfamoylamino groups such as dimethylsulfamoylamino group; arylsulfamoylamino groups such as N-phenylsulfamoylamino group; and acylamino groups (eg, alkylcarbonylamino groups such as acetylamino group and myristoylamino group) Groups; arylcarbonylamino groups such as benzoylamino group, etc .; ureido groups (eg, alkylureido groups such as N, N-dimethylaminoureide group; N-phenylureido group, N- (p-cyanophenyl) ureido group, etc. Riruureido group), an alkylthio group (e.g. methylthio group, t-octylthio group), an arylthio group (e.g., phenylthio group), and heterocyclic thio group (e.g., 1-phenyl-tetrazole -5
-Thio group, 5-methyl-1,3,4-oxadiazole-2-thio group, etc.).

Examples of the halogen atom represented by R _B include a chlorine atom and a fluorine atom, and among them, a chlorine atom is preferable.

Examples of the alkoxy group represented by R _B include methoxy, ethoxy, i-propoxy, butoxy, octyloxy, dodecyloxy and the like.

Examples of the group that can be substituted on the benzene ring represented by R _C include a halogen atom, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, Examples include alkylsulfonyl, ureido, sulfamoylanomi, alkoxycarbonylamino, alkoxysulfonyl, acyloxy, nitro, heterocyclic, cyano, acyl, alkylsulfonyloxy, and arylsulfonyloxy. Further, these groups capable of substituting on the benzene ring represented by R _C may further have a substituent, and examples of the substituent include those represented by R in the aforementioned general formula (II).
Examples of the group include the same groups as the groups exemplified as the substituents for the aliphatic group, aromatic group, and heterocyclic group represented by _A.

[0041] Examples of the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _D, heterocyclic group bonded to a coupling active site via a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, Examples thereof include an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halogen atom and the like, and a heterocyclic group and an aryloxy group bonded to a coupling active site by a nitrogen atom are preferable.

The yellow coupler represented by formula (II) according to the present invention can be used alone or in combination of two or more, and can be used in combination with other known yellow couplers. Further, the yellow coupler according to the present invention,
Usually, it can be used in the range of about 1 × 10 ^-3 mol to about 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide.

The following are typical examples of the yellow coupler represented by formula (II) of the present invention, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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Next, the magenta coupler represented by formula (III) of the present invention will be described. In the general formula (III), the substituent represented by R _S is not particularly limited,
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Each group such as alkenyl and cycloalkyl is exemplified,
In addition to this, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide,
Examples include ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group represented by R _S is preferably one having 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R _S is preferably a phenyl group. Examples of the acylamino group represented by R _S include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R _S include an alkylsulfonylamino group and an arylsulfonylamino group.

[0062] alkylthio group represented by R _S, the alkyl moiety in the arylthio group, the aryl component is the R _S
And an alkyl group and an aryl group represented by

The alkenyl group represented by R _S is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. Good.

The cycloalkenyl group represented by R _S has preferably 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

As the sulfonyl group represented by R _S , an alkylsulfonyl group, an arylsulfonyl group and the like; a sulfinyl group as an alkylsulfinyl group and an arylsulfinyl group; and as the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group and an aryl An oxyphosphonyl group, an arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group, arylsulfa A moyl group, etc .; an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; a ureido group, an alkylureido group, an arylureido group, etc .; a sulfamoylamino group, a Kill sulfamoylamino group, an aryl sulfamoylamino group or the like; 5 is a heterocyclic group
Preferred is a 7-membered one, specifically a 2-furyl group, 2-
A thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; the heterocyclic oxy group preferably has a 5- to 7-membered heterocyclic ring, for example, 3,4,5,6-tetrahydropyranyl-2-oxy Group, 1-phenyltetrazol-5-oxy group and the like; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4- Diphenoxy-1,3,5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group and 3-heptadecylsuccinimide Group, phthalimide group, glutarimide group, etc .; spiro compound residues include spiro [3.3] heptan-1-yl, etc .; bridged hydrocarbon compound Examples of the group bicyclo [2.
2.1] Heptan-1-yl, tricyclo [3.3.
1.1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

Examples of the atoms and groups which can be eliminated by the reaction with the oxidized form of the color developing agent represented by X ₀ include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0067]

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(R ₁ 'has the same meaning as R _S , Z' has the same meaning as Y in formula (III), and R ₂ 'and R _2
3 'represents a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group. And the like, and preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Y or Z 'include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring. The substituent which the ring may have is R. What mentioned about _S is mentioned.

The specific examples of the compounds represented by formula (III) of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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Next, the cyan coupler represented by formula (IV) contained in the color photographic light-sensitive material of the present invention will be described.

In formula (IV), the alkyl group having 2 to 6 carbon atoms represented by R _T may be linear or branched, and includes those having a substituent.

The ballast group represented by R _U is an organic group having a size and shape that provides sufficient bulk to the coupler molecule to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to another layer. is there. Preferred examples of the ballast group are represented by the following general formula.

General formula —CH (RC) —O—Ar where RC represents an alkyl group having 1 to 12 carbon atoms.
Represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X include an alkyloxy group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, Examples include a ring oxy group, a heterocyclic group bonded to a coupling active site with a nitrogen atom, a halogen atom and the like, and a halogen atom, a substituted alkyloxy group, an aryloxy group and the like are preferable.

Next, specific examples of the coupler represented by the general formula (IV) are shown, but are not limited thereto.

[0091]

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[0092]

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[0093]

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Next, the general formula (V) and the general formula (V
The cyan coupler represented by I) will be described in detail.

In the above general formulas (V) and (VI), the branched alkyl groups represented by R _V and R _X are i-propyl, t-butyl, sec-butyl, i-butyl, A t-octyl group and the like can be mentioned.

The alkyl component of the substituted alkyl group includes
It may be a linear, branched or cyclic alkyl group, and may be a methyl group, an ethyl group, a butyl group, an i-propyl group, a t-butyl group, a sec-butyl group, an i-butyl group, a t-octyl group, a cyclohexyl group, or the like. Can be mentioned.

The aryl component of the substituted aryl group includes
A phenyl group and the like can be mentioned.

The heterocyclic group includes 2-furyl, 2-thienyl, 2-imidazolyl, 2-thiazolyl, 3
-Isoxazolyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 3-pyrazolyl group, 2-benzothiazolyl group and the like.

However, when R _V and R _X represent a substituted alkyl group or a substituted aryl group, these alkyl and aryl components necessarily have a substituent.

When R _V and R _{X each} represent a branched alkyl group or a heterocyclic group, these groups may have a substituent atom or a substituent, if necessary.

The substituent atoms and substituents are not particularly limited, but typically include groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. , Besides this, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, aryloxy, heterocyclic oxy,
Siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, Mercapto,
Examples include groups such as nitro and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

In the general formulas (V) and (VI),
There are no particular limitations on the substituent represented by R _W and R _Y, typically, alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, there may be mentioned the groups cycloalkyl or the like, In addition to this, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo and other groups, And spiro compound residues, bridged hydrocarbon compound residues, and the like. These groups may be further substituted by the above substituents.

In the above-mentioned substituents on the branched alkyl group, substituted alkyl group, substituted aryl group or heterocyclic group represented by R _V and R _X , and the substituents represented by R _W and R _Y , As the alkyl group, those having 1 to 32 carbon atoms are preferable,
It may be linear or branched.

The aryl group is preferably a phenyl group. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituents represented by R _W and R _Y , respectively.

The alkenyl group is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched.

The cycloalkenyl group may have 3 to 3 carbon atoms.
12, especially 5-7 are preferred.

As the sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, etc .; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .;
Examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an arylphosphonyl group; acyl groups include an alkylcarbonyl group and an arylcarbonyl group; and carbamoyl groups include an alkylcarbamoyl group and an arylcarbamoyl group. Etc .; sulfamoyl groups as alkylsulfamoyl groups, arylsulfamoyl groups, etc .; acyloxy groups as alkylcarbonyloxy groups, arylcarbonyloxy groups, etc .; sulfonyloxy groups as alkylsulfonyloxy groups, arylsulfonyloxy groups, etc. A carbamoyloxy group such as an alkylcarbamoyloxy group and an arylcarbamoyloxy group; a ureido group such as an alkylureido group and an arylureido group; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-
Benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group , A 1-phenyltetrazole-5-oxy group and the like; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy group. -1,3,5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group and 3-heptadecylsuccinimide group , Phthalimide group, glutarimide group, etc .; spiro compound residues include spiro [3.3] heptan-1-yl, etc .; bridged hydrocarbon compounds Examples of the group bicyclo [2.
2.1] heptane-1-yl, tricyclo [3.3.
1.1 ^3.7 ] decan-1-yl, 7.7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

[0110] As the substituent represented by R _W and R _Y is an alkyl group is preferably an aryl group, an aryl group is particularly preferred.

The above group may further have a substituent such as a non-diffusible group such as a long-chain hydrocarbon group or a polymer residue.

Examples of the atoms and groups which can be eliminated by the reaction with the oxidized form of the color developing agent represented by X ₁ and X ₂ include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkoxy, an aryloxy and a hetero atom. Ring oxy, acyloxy,
Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples include acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl. X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group bonded by an N atom, or the like.

The specific examples of the cyan couplers represented by the general formulas (V) and (VI) are shown below. However, the cyan coupler of the present invention is not limited to these.

[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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In order to incorporate the cyan coupler of the present invention into the light-sensitive material of the present invention, known techniques used for ordinary cyan couplers can be applied. It is preferable to dissolve the coupler in a high-boiling solvent and, if necessary, in combination with a low-boiling solvent, to disperse the fine particles, and to add them to the silver halide emulsion of the present invention. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent and the like may be used in combination.

The silver halide emulsion used in the present invention is a silver halide color photographic emulsion known in the art.

In the silver halide photographic light-sensitive material of the present invention,
The hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.

The silver halide photographic light-sensitive material of the present invention may further contain various photographic additives. For example, antifoggants, development accelerators, development retarders, bleaching accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants Agents, plasticizers, wetting agents and the like (RD17
643).

Further, the development accelerator, bleaching accelerator, developer, silver halide solvent, toning agent, hardener, fogging agent, antifogging agent, Compounds that release photographically useful fragments can be used, such as sensitizers, spectral sensitizers, and desensitizers.

The support of the silver halide photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, polyester film such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyamide film, polycarbonate Film, polystyrene film, etc.
In the case of a transparent support, a reflective layer may be used in combination.

These supports are appropriately selected according to the intended use of the light-sensitive material. Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layer and other constituent layers used in the present invention. U.S. Pat.
It is also possible to use a simultaneous coating method of two or more layers by the method described in JP-A-81,791 and JP-A-2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined, but from the support side, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are sequentially arranged. It is preferable to use an array of

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer are formed. The layers can be used in appropriate combination. A hydrophilic colloid can be used as a binder in these constituent layers, and gelatin is preferably used. In addition, various photographic additives described in the description of the emulsion layer can be contained in the layer.

The processing method of the photographic material using the silver halide emulsion used in the present invention is not particularly limited, and any generally known processing method can be applied.
For example, typical examples thereof include a method of performing bleach-fixing after color development, and further performing washing and / or stabilization if necessary. After color development, performing bleaching and fixing separately, and further washing with water as necessary. The silver halide color photographic light-sensitive material of the present invention can be rapidly processed in the steps of color development, bleach-fixing, and washing (or stabilization). Suitable to be processed.

[0137]

EXAMPLES The present invention will be specifically described below with reference to Examples.
The present invention is not limited to this.

Example 1 Polyethylene was laminated on one side of a paper support, and polyethylene having titanium oxide was laminated on the other side. On the support, each layer having the following structure was replaced with a polyethylene layer containing titanium oxide. And a multilayer color photosensitive material sample 1 was prepared. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 of (ST-2)
g, additive (HQ-1) 0.67 g, irradiation prevention dye (AI-3) 0.33 g, high boiling organic solvent (D
(NP) 6.67 g was dissolved by adding 60 ml of ethyl acetate.
This solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions 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. (H-1) was added to the second and fourth layers as a hardener, and (H-2) was added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount of addition in the light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0141]

[Table 1]

[0142]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2 , 5-Di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) tylhydroquinone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0144]

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[0145]

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[0146]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
In 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C,
The following (solution A) and (solution B) were subjected to pAg = 6.5, pH =
At the same time over 30 minutes while controlling to 3.0,
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH is controlled using an aqueous solution of sulfuric acid or sodium hydroxide, and pAg
For the control, a control liquid having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control liquid is solution A,
When mixing liquid B, 0.1 mol / liter, liquid C,
When mixing the liquid D, it was 1 mol / l.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Water was added to make 200 ml.

(Solution B) 10 g of silver nitrate was added to make up to 200 ml.

(Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make up to 600 ml.

(Solution D) Silver nitrate 300 g Water was added to make up to 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
After desalting using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compound was used for EMP-2.
Chemical ripening was performed at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation method of red-sensitive silver halide emulsion) (Solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was synthesized using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- (3-acetamido) phenyl-5-mercaptotetrazole

[0159]

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The yellow coupler (Y-
1), the third layer magenta coupler (M-1), and the fifth layer
The cyan coupler (C-1) in each layer was changed to an equimolar amount of the combination shown in Table 3, and the fourth layer and the sixth layer each contained 0.5 g / m ² of the compound of the present invention in the same amount of DOP. Samples 2 to 25 were prepared in the same manner except that they were dissolved, dispersed and added as shown in Table 3.

The properties of the thus obtained samples were evaluated by the following methods. << Lightfastness >> Each of the above samples was exposed to white light through an optical wedge, and then subjected to a color development process in the following processing steps. A fade test was performed on each of the obtained samples for 10 days using a fade meter, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined using blue, green, and red light.

<< Color Reproducibility >> First, a color checker manufactured by Macbeth was photographed using a color negative film (Konica Color LV-400: manufactured by Konica) and a camera (Konica FT-1: manufactured by Konica). Subsequently, color negative development processing (CNK-4: manufactured by Konica) was performed, and the obtained negative image was printed on each sample to a size of 82 mm × 117 mm using a Konica color printer (CL-P2000: manufactured by Konica). (Printer conditions were set for each sample so that the gray on the color checker became gray on the print). The color reproducibility of the obtained practical prints was visually evaluated by 20 persons, and the evaluation results were shown in the following five grades.

5: All 20 persons are evaluated as being good 4: 15 to 19 persons are evaluated as being good 3: 10 to 14 persons are evaluated as being good 2: 5 to 9 persons are evaluated as being good Evaluation 1: 0 to 4 out of 20 were evaluated as good Color development processing Processing time Temperature Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30 to 34 ° C. 90 seconds Drying 60 to 80 ° C. 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene -1,1-diphosphonic acid 1.0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g N-ethyl- N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g Optical brightener (4,4′-diaminostilbenesulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water To make the total volume 1 liter, and adjust the pH to 10.10.

Bleaching / fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Adjust to pH = 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzoisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g The total volume is adjusted to 1 liter by adding water, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Table 3 also shows the results.

[0167]

[Table 3]

As is clear from the results in Table 3, Samples 1, 3 to 10 outside the present invention have insufficient color reproducibility.
Insufficient light fastness. Samples 11 to 25 using the coupler of the present invention and the compound of the present invention all have good color reproducibility and very good light fastness.

[0169]

As demonstrated in the examples, the silver halide color photographic light-sensitive material according to the present invention has an excellent effect on color reproducibility and also excellent light resistance of a dye image.

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
A photographic constituent layer including a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and an intermediate layer, wherein at least one of the photographic constituent layers contains at least a compound represented by the following formula (I): A silver halide color photographic light-sensitive material characterized by containing one kind. Embedded image [Wherein, R ¹ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group or a heterocyclic group, R ² represents an alkyl group having 1 to 12 carbon atoms, R ³
And R ⁴ each represent a group that can be substituted on a benzene ring, m represents an integer of 0 to 2, and when m is 2, a plurality of R ³ may be the same or different. n represents an integer of 0 to 5,
When n is 2 or more, a plurality of R ⁴ may be the same or different. ] 2. A blue-sensitive silver halide emulsion layer on a support,
A blue-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a photographic component layer including an intermediate layer, wherein the blue-sensitive silver halide emulsion layer contains at least a yellow coupler represented by the following formula (II): A silver halide color photographic light-sensitive material comprising at least one compound, and at least one of the compounds represented by formula (I) in at least one of the photographic constituent layers. Embedded image [Wherein, R _A represents an aliphatic group, an aromatic group or a heterocyclic group, R _B represents a hydrogen atom, a halogen atom or an alkoxy group, R _C represents a group capable of being substituted on a benzene ring, p Represents an integer of 0, 1 or 2, and when p is 2, a plurality of R
_C may be the same or different. _XD represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ] 3. A blue-sensitive silver halide emulsion layer on a support,
Green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer
And a photographic constituent layer including an intermediate layer,
Magenta represented by the following general formula (III) in the silver halide emulsion layer
At least one of the pullers, and
A compound represented by the general formula (I) in at least one layer
Halogen containing at least one of the following:
Silver halide color photographic material. Embedded image[Wherein, R_SRepresents a hydrogen atom or a substituent, and Y represents nitrogen-containing
Represents a group of nonmetallic atoms necessary for forming a heterocyclic ring,
The ring formed by may have a substituent. X ₀Is water
Released by reaction with elemental atom or oxidized form of color developing agent
Represents a group. ] 4. A blue-sensitive silver halide emulsion layer on a support,
A photographic constituent layer including a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and an intermediate layer, wherein the red-sensitive silver halide emulsion layer has the following general formula (IV), (V) or (VI) Wherein at least one of the cyan couplers represented by formula (I) is contained, and at least one of the compounds represented by formula (I) is contained in at least one of the photographic constituent layers. Silver color photographic light-sensitive material. Embedded image [In the formula, R _T represents an alkyl group having 2 to 6 carbon atoms, R _U represents a ballast group, and X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. [Chemical formula 5] Wherein, R _V and R _X are each branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R _W and R _Y
Represents a substituent, and X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ]