JPH0980708A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material containing a cyan coupler capable of improving hue and enhancing image quality. SOLUTION: The color photographic sensitive material contains, in at least one layer on a support, the coupler represented by the formula in which Cp1 is a coupler residue able to form a dye and to release it from the photosensitive material during its processing by reaction with the oxidation product of a color developing agent; T is a bonding group to be released from Cp1 by coupling of Cp1 with the oxidation product of the agent and then to release the Cp2 part; (n) is 0 or 1; and Cp2 is a coupler residue.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide color photographic light-sensitive material. More specifically, it relates to a silver halide color photographic light-sensitive material containing a cyan coupler which has a good hue and can achieve high image quality.

[0002]

2. Description of the Related Art In silver halide color light-sensitive materials,
Using the exposed silver halide as an oxidant, the oxidized aromatic primary amine color developing agent and the coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and dyes related thereto. It is well known that a color image is formed. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta, and cyan dyes. Of these, phenol- or naphthol-based couplers have hitherto been generally used for forming a cyan image. However, since these couplers have an unfavorable absorption in the green region, they have a serious problem that the color reproducibility is significantly reduced.

As couplers for solving this problem, the pyrrolotriazoles described in European Patent Publication Nos. 491197A1, 488248 and 545300 have been proposed. Needless to say, the characteristics of these couplers are that the hue of the dye formed by the coupling reaction with the oxidized product of the color developing agent is excellent, but other characteristics are that the coupling activity is high and the dye formed. Is high (about 2 to 3 times that of a dye obtained from a phenol and naphthol type coupler). However, when the pyrrolotriazoles described in these patents are used, there is a problem that granularity and sharpness are deteriorated. In particular, there is a problem that the sensitivity is lowered in the process of color reversal in which color development is performed after black and white development, and it has been desired to solve these problems.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material containing a cyan coupler having a good hue and capable of achieving high image quality.

[0005]

The object of the present invention is achieved by a silver halide color light-sensitive material characterized in that at least one layer on a support contains a coupler represented by the following general formula (1). It was

[0006]

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In the general formula (1), Cp ₁ represents a coupler residue capable of reacting with an oxidized product of a color developing agent to form a dye flowing out from a photographic light-sensitive material during processing. T is Cp
₁ represents a linking group which is released from the Cp ₁ portion by coupling of ₁ with an oxidized product of a color developing agent and can subsequently release the Cp ₂ portion, and n represents 0 or 1. Cp ₂ represents a coupler residue represented by the following general formula.

[0008]

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In the general formulas (2-1) to (2-5), R
₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.2 or more and 1.00 or less, and R ₃ represents a substituent. General formula (2-1), (2-2), (2-4)
In the formula, X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent. General formula (2-
In 3) and (2-5), G represents a hydrogen atom or a blocking group which can be removed by hydrolysis during a photographic process or an intramolecular nucleophilic substitution reaction.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below in detail. In the general formula (1), Cp ₁ represents a coupler residue capable of reacting with an oxidized product of a color developing agent to form a dye flowing out from the photographic light-sensitive material during processing. Examples of such a coupler residue include yellow (for example, benzoylacetanilide yellow coupler, pivaloylacetanilide yellow coupler, malondiamide yellow coupler) and magenta (for example, pyrazolone magenta coupler) which are usually used in silver halide photographic light-sensitive materials. , Pyrazoloazole-based magenta couplers), cyan (phenolic cyan couplers, naphthol-based cyan couplers, pyrroloazole-based cyan couplers) among the coupler residues that do not have a ballast group (diffusion resistant group) You can choose from. Preferred Cp ₁ includes the following general formula (1-1) or general formula (1-2).

[0011]

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The general formula (1-1) will be described in detail below. G ₁ represents a hydrogen atom or a blocking group which can be split off by hydrolysis during a photographic process or an intramolecular nucleophilic substitution reaction. Typical examples of the Broking group which can be eliminated by hydrolysis include, for example, U.S. Pat.
2706685, 2865748, 4123281, etc. are mentioned. Further, as a typical example of the Broking group which can be eliminated by an intramolecular nucleophilic substitution reaction, for example, those described in JP-A-55-53330 can be mentioned.
G ₁ is preferably a hydrogen atom.

R ₄ represents a group capable of substituting for naphthalene,
n ₁ represents an integer of 0-4. R ₄ is, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (preferably a linear or branched alkyl group having 6 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl). , T-butyl), a cycloalkyl group (preferably a cycloalkyl group having 6 or less carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group (preferably an alkenyl group having 6 or less carbon atoms, for example, vinyl, allyl). , 3-buten-1-yl), an aryl group (preferably an aryl group having 10 or less carbon atoms, for example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably 6 or less carbon atoms, 5 To 8-membered heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazo Group, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably an alkoxy group having 6 or less carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy),

Cycloalkyloxy groups (preferably cycloalkyloxy groups having 6 or less carbon atoms, for example, cyclopentyloxy, cyclopropyloxy, cyclohexyloxy), aryloxy groups (preferably having 10 carbon atoms).
The following aryloxy groups such as phenoxy and 2-naphthoxy, heterocyclic oxy groups (preferably heterocyclic oxy groups having 6 or less carbon atoms, such as 1-phenyltetrazole-5-oxy and 2-tetrahydropyranyl Oxy, 2-furyloxy), a silyloxy group (preferably a silyloxy group having 6 or less carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), an acyloxy group (preferably an acyloxy group having 10 or less carbon atoms, for example, , Acetoxy, pivaloyloxy, benzoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 10 or less carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), a cycloalkoxycarbonyloxy group (preferably having a carbon number). 10 or less A chloroalkoxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 10 or less carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group (preferably having a carbon number). A carbamoyloxy group having 10 or less, for example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 10 or less carbon atoms, for example, N, N -Diethylsulfamoyloxy, N-propylsulfamoyloxy),
An alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 6 or less carbon atoms, for example, methanesulfonyloxy, butanesulfonyloxy), an arenesulfonyloxy group (preferably an arenesulfonyloxy group having 10 or less carbon atoms, for example, benzene Sulfonyloxy), an acyl group (preferably an acyl group having 10 or less carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl),

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 10 or less carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl), a cycloalkyloxycarbonyl group (preferably a cycloalkyloxycarbonyl group having 10 or less carbon atoms, for example, A cyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 10 or less carbon atoms, for example, phenoxycarbonyl), a carbamoyl group (a carbamoyl group having 10 or less carbon atoms, for example, carbamoyl, N, N-). Dimethylcarbamoyl, N
-Propylcarbamoyl), a sulfamoyl group (preferably a sulfamoyl group having 10 or less carbon atoms, for example, sulfamoyl, N, N-dimethylsulfamoyl, N-
Ethylsulfamoyl, N-phenylsulfamoyl), amino group (preferably an amino group having 6 or less carbon atoms, for example, amino, methylamino, N, N-diethylamino), anilino group (preferably 10 or less carbon atoms) Anilino group of, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 10 or less carbon atoms, for example, 4-pyridylamino group),
An acylamino group (preferably an acylamino group having 10 or less carbon atoms, such as acetamide or benzamide), an ureido group (preferably an ureido group having 10 or less carbon atoms,
For example, NN dimethylureido, N-phenylureido), imide group (preferably an imide group having 10 or less carbon atoms, for example, N-succinimide group, N-phthalimide), alkoxycarbonylamino group (preferably 10 carbon atoms). The following alkoxycarbonylamino groups, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino),

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 10 or less carbon atoms, for example, a phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 10 or less carbon atoms, for example, methane Sulfonamide, ethanesulfonamide, benzenesulfonamide), a sulfamoylamino group (preferably a sulfamoylamino group having 10 or less carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethylsulfamoyl) Amino), an azo group (preferably an azo group having 10 or less carbon atoms, for example,
Phenylazo), alkylthio groups (preferably having 6 carbon atoms)
The following alkylthio groups, for example, methylthio, ethylthio, arylthio groups (preferably arylthio groups having 10 or less carbon atoms, for example, phenylthio), heterocyclic thio groups (preferably heterocyclic thio groups having 10 or less carbon atoms, For example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 10 or less carbon atoms, for example, butanesulfinyl), an arenesulfinyl group (preferably carbon). An arene sulfinyl group having 10 or less, for example, benzenesulfinyl), an alkanesulfonyl group (preferably an alkanesulfonyl group having 6 or less carbon atoms, for example, methanesulfonyl, ethanesulfonyl), an arenesulfonyl group (preferably 10 or less carbon atoms) The arenes In Honiru group, e.g., benzenesulfonyl, 1-naphthalenesulfonyl), a sulfo group,
A phosphonyl group (preferably a phosphonyl group having 10 or less carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl) is represented.

The substituent represented by R ₄ may further have a substituent, and a preferable substituent is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group,
Hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfa Moyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamide group, alkoxy Carbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, azo group, mercapto group, alkylthio group, aryl O group, a heterocyclic thio group, a sulfinyl group, a sulfo group, an alkanesulfonyl group, arenesulfonyl group, a sulfamoyl group, and a phosphonyl group.

R ₅ is a hydrogen atom, --SO ₂ R ₅₁ , --CO ₂
R _52, -CN, -CONHR _53, a group represented by -NHCOR ₅₄ or the following general formula (1-1-1).

[0019]

[Chemical 6]

R ₅₁ represents a hydroxyl group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an amino group, an anilino group, a heterocyclic amino group, an alkylthio group or an arylthio group, and R ₅₂ represents a hydrogen atom, an alkyl group or an aryl group. Represents a group or a heterocyclic group. Preferred specific examples of the group represented by R ₅₁ and R ₅₂ are the same as those described in the description of the group represented by R ₄ . R ₅₃ and R ₅₄ represent a hydrogen atom, an alkyl group (having 4 or less carbon atoms), a phenyl group, a heterocyclic group (having 6 or less carbon atoms) or a group represented by the following general formula (1-1-2).

[0021]

[Chemical 7]

Examples of the alkyl group having 4 or less carbon atoms represented by R ₅₃ and R ₅₄ include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl and isobutyl.
Examples of the heterocyclic group having 6 or less carbon atoms represented by R ₅₃ and R ₅₄ include 2-thienyl, 4-pyridyl, 2-furyl and 2
-Pyridyl and 3-pyridyl can be mentioned. R ₅₃ and R ₅₄
The alkyl group (having 4 or less carbon atoms), the phenyl group and the heterocyclic group (having 6 or less carbon atoms) represented by may further have a substituent, and a halogen atom (for example, a fluorine atom or a chlorine atom) is preferable as a substituent. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, a sulfo group, an alkoxy group (for example, methoxy and ethoxy for an alkoxy group having 1 to 3 carbon atoms), an alkoxycarbonyloxy group (for an alkoxycarbonyloxy group having 6 or less carbon atoms). , For example, methoxycarbonyloxy), a carbamoyloxy group (a group having 6 or less carbon atoms, for example, N, N-dimethylcarbamoyloxy), a sulfamoyloxy group (for a group having 6 or less carbon atoms, for example, N, N-dimethyl) Sulfamoyloxy), sulfonyloxy group (groups having 6 or less carbon atoms, such as methanesulfonyloxy) (E.g. having 6 or less of group carbon, acetyl) acyl group, an alkoxycarbonyl group (having a carbon number 6
The following groups are, for example, methoxycarbonyl, aryloxycarbonyl groups (for example, phenoxycarbonyl for groups having 10 or less carbon atoms), carbamoyl groups (for example, carbamoyl and N-methylcarbamoyl for groups having 6 or less carbon atoms), amino groups. (A group having 6 or less carbon atoms, such as amino,
N-methylamino), an amide group (a group having 10 or less carbon atoms such as acetamide), an alkoxycarbonylamino group (a group having 6 or less carbon atoms such as methoxycarbonylamino), an ureido group, a sulfonamide group (having 10 carbon atoms). The following groups include, for example, methanesulfonamide), sulfamoylamino groups (for groups having 6 or less carbon atoms, such as N, N-dimethylsulfamoylamino), sulfonyl groups (for groups having 10 or less carbon atoms, such as methane). Sulfonyl).

R ₅₁ is an alkoxy group, an aryloxy group,
When it is a heterocyclic oxy group, an amino group, an anilino group, a heterocyclic amino group, an alkylthio group, an arylthio group,
R ₅₁ may further have a substituent, and preferable substituents are the same as those exemplified as the preferable substituents of the groups represented by R ₅₃ and R ₅₄ . R ₅₂ is an alkyl group,
When representing an aryl group or a heterocyclic group, R ₅₂ may further have a substituent, and preferable substituents are the same as those mentioned as the preferable substituents of the groups represented by R ₅₃ and R _54. is there.

R ₅₁ is preferably a hydroxyl group, an alkoxy group, an amino group or an anilino group, and particularly preferably,
An amino group and an anilino group. R ₅₂ is preferably a hydrogen atom or an alkyl group. R ₅₃ and R ₅₄ are preferably a hydrogen atom and an alkyl group, and particularly preferably a methyl group and an ethyl group. Particularly preferred substituents for the alkyl group, phenyl group and heterocyclic group represented by R ₅₃ and R ₅₄ are a cyano group, an amide group, a sulfonamide group, a sulfo group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, A carboxyl group, a hydroxyl group, and a sulfonyl group.

In the general formula (1-1-1), R ₅₅ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms (eg, methyl, ethyl, propyl, isopropyl, t-butyl). R ₅₇ represents an organic group having 1 to 10 carbon atoms, preferably an alkyl group (an alkyl group having 6 or less carbon atoms such as methyl and ethyl), an aryl group (an aryl group having 10 or less carbon atoms such as phenyl, p -Tolyl), hydroxyl group, alkoxy group (alkoxy group having 6 or less carbon atoms, for example, methoxy, ethoxy), aryloxy group (aryloxy group having 10 or less carbon atoms, for example, phenoxy, 4-methoxyphenoxy, 4 -Nitrophenoxy), a heterocyclic oxy group (a heterocyclic oxy group having 6 or less carbon atoms,
For example, 2-furyloxy), an amino group (an amino group having 6 or less carbon atoms, such as amino, N-methylamino, N,
N-dimethylamino), anilino group (anilino group having 10 or less carbon atoms, for example, N-methylanilino), heterocyclic amino (heterocyclic amino group having 6 or less carbon atoms, for example, 4-pyridylamino, alkylthio group (carbon An alkylthio group having a number of 6 or less, such as ethylthio, or arylthio (an arylthio group having a carbon number of 10 or less, such as phenylthio) is represented, A ₁ and A ₂ each represent CO or SO _2, and n ₂ is 0. 1 or 2, preferably 0 or 1. R ₅₆ is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene group or-.
It represents {C (R ₅₈ ) R ₅₉ } n ₃ −. When R ₅₆ is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene group, these phenylene groups are -N (R ₅₅ )-, and A ₁
It may have a substituent other than the above, and a preferable substituent is R
It is the same as the one mentioned as the group represented by ₄ .

R ₅₈ and R ₅₉ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl).
And these alkyl groups may have a substituent such as a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy), an alkylthio group (for example, methylthio), an alkoxycarbonyl group (for example, methoxycarbonyl), n ₃ represents an integer of 1 to 3. General formula (1-
In 1-1), R ₅₅ is preferably a hydrogen atom or a methyl group. Preferred as R ₅₆ is a methylene group,
Ethylene group, 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group. Particularly preferred groups as R ₅₇ are an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group and an anilino group.

In the general formula (1-1-2), W ₂ is -C.
Represents ON (R ₄₅ )-or -CO _2- . R ₄₁ , R ₄₂ , R
₄₃ and R ₄₄ represent a group having the same meaning as the group represented by R ₄ , R ₄₅ represents a hydrogen atom or an alkyl group (eg, methyl, ethyl, propyl), and these groups further have a substituent. The preferred substituents are the same as those listed as the preferred substituents of the group represented by R ₅₃ . R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₅ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, and more preferably a hydrogen atom or a methyl group. R ₄₆ represents an alkyl group having 3 or less carbon atoms (eg, methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, trifluoroethyl), and preferably a methyl group or an ethyl group. n ₄ , n ₅ are 1, 2 or 3 respectively
And is preferably 1 or 2.

The general formula (1-2) will be described in detail below. R ₆ is -COR ₆₁ , -CO ₂ R ₆₂ , -CONH
R ₆₃ , a nitro group, a cyano group, and general formula (1-2
It represents a heterocyclic group represented by 1).

[0029]

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R ₆₁ , R ₆₂ and R ₆₃ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₆₁ , R ₆₂
And preferred examples of the alkyl group, aryl group and heterocyclic group represented by R ₆₃ are the same as those described in the description of the group represented by R ₃ , and these groups further have a substituent. May be. Preferred substituents are the same as the preferred substituents described for the groups represented by R ₅₃ and R ₅₄ above.

In the general formula (1-2-1), Q ₁ represents a nitrogen atom or C (R ₆₄ ), and R ₆₄ represents a group having the same meaning as the group represented by R ₄ . Q ₂ represents an oxygen atom, a sulfur atom or N (R ₆₅ ), R ₆₅ is a group substitutable on the nitrogen atom, for example, the groups represented by R ₅₃ and R ₅₄ above,
Hydroxyl group, carboxyl group, sulfo group, acyl group (for example, acetyl for groups having 6 or less carbon atoms), alkoxycarbonyl group (for example, for example, methoxycarbonyl for groups having 6 or less carbon atoms), aryloxycarbonyl group (having 10 carbon atoms).
The following groups include, for example, phenoxycarbonyl, carbamoyl groups (groups having 6 or less carbon atoms, such as carbamoyl, N
-Methylcarbamoyl) and a sulfonyl group (a group having 10 or less carbon atoms, for example, methanesulfonyl). Z
₁ represents a non-metal atom group necessary for forming a 5- or 6-membered ring. The non-metallic atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably a carbon atom. The heterocycle represented by formula (1-2-1) may be condensed with another ring or may have a substituent. Preferred substituents are the same as the preferred substituents described for the groups represented by R ₅₃ and R ₅₄ above.

R ₇ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably a linear or branched alkyl group having 6 or less carbon atoms, for example, methyl, ethyl, propyl). , Isopropyl,
Butyl, t-butyl), a cycloalkyl group (preferably a cycloalkyl group having 6 or less carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group (preferably an alkenyl group having 6 or less carbon atoms, for example, vinyl, Allyl, 3-buten-1-yl), aryl group (preferably aryl group having 10 or less carbon atoms, for example, phenyl, 1-naphthyl, 2-naphthyl), alkoxy group (preferably alkoxy group having 6 or less carbon atoms) And, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy), a cycloalkyloxy group (preferably a cycloalkyloxy group having 6 or less carbon atoms, for example, cyclopentyloxy, cyclopropyloxy). , Cyclohexyloxy), aryloxy groups (preferably having 10 or less carbon atoms) Aryloxy group, e.g., phenoxy, 2-naphthoxy), an acyloxy group (preferably an acyloxy group having not more than 10 carbon atoms, for example,
Acetoxy, pivaloyloxy, benzoyloxy) and the substituents mentioned for R ₆ .

Next,-(T) _m -will be described in detail. T represents a linking group which is released from Cp ₁ by coupling between Cp ₁ and an oxidized color developing agent, and is capable of subsequently releasing the Cp ₂ portion, and is represented by the following general formula (3). it can. m represents 0 or 1.

[0034]

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T ₁ and T ₃ are represented by the following general formula (3-1)-
It is a linking group represented by (3-3).

[0036]

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R ₈₁ and R ₈₂ are each a hydrogen atom, an alkyl group (an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, t-octyl, octadecyl) or an aryl group ( An aryl group having 24 or less carbon atoms, for example, phenyl, 1
-Naphthyl, 2-naphthyl). The alkyl group and aryl group represented by R ₈₁ and R ₈₂ may be substituted with a substituent represented by R ₃ described later. R ₈₁ and R ₈₂ are preferably hydrogen atoms.

R ₈₃ and R ₈₄ have the same meaning as the groups represented by R ₈₁ and R ₈₂ above. R ₈₅ represents a group having the same meaning as the groups represented by R ₈₁ and R ₈₂ above, but preferably at least one electron-withdrawing group (for example, R ₁ described below).
And a methyl group (eg, cyanomethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl) substituted with an electron-withdrawing group represented by R ₂ . T ₂ is U.S. Pat. Nos. 4,248,982, 4,861,701, 4,857,440;
And a timing group utilizing an intramolecular nucleophilic substitution reaction such as described in JP-A-57-56837 or the like.
Represents a timing group utilizing an electron transfer reaction along a conjugated chain as described in 56-114946, 57-154234 and 57-188035. m ₁ , m ₂ and m ₃ each independently represent 0 or 1. When m is 0, Cp ₁ and C
P ₂ is linked so that Cp ₂ is released only when Cp ₁ and the oxidized developer are coupled.

Next, Cp₂Will be described in detail. Cp
₂Is a coupler represented by the general formula (2-1) to (2-5)
Residue. Cp ₂Are preferably of the general formula (2-1) and
And a coupler residue represented by (2-3), and particularly preferred
Or a coupler residue represented by the general formula (2-1).
You.

R in the general formulas (2-1) to (2-5)
₁ and R ₂ both have Hammett's substituent constant σ _p values
The electron withdrawing group is 0.2 or more and 1.00 or less, but R ₁ and R ₂
It is preferable that the sum of and is 0.65 or more. The coupler of the present invention has excellent performance as a cyan coupler by introducing such a strong electron-withdrawing group. The sum of the σ _p values of R ₁ and R ₂ is preferably 0.7 or more, and the upper limit is about 1.8.

In the present invention, R ₁ and R ₂ have a Hammett substituent constant σ _p value (hereinafter, simply referred to as σ _p value) of 0.2.
The electron withdrawing group is 1.00 or less. Preferably, σ _p
It is an electron-withdrawing group having a value of 0.3 or more and 0.80 or less. Hammett's rule was published in 1935 in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. Hamm
A rule of thumb put forward by Ett, this is widely accepted today. Substituent constants determined by the Hammett rule include σ _p values and σ _m values, and these values are described in many general textbooks.
A. Dean, "Lange's Handbook of Chemistry", 12th Edition, 1979 (McGraw-Hill) and "Chemical Area Special Issue", No. 122, pp. 96-103, 1979 (Nankodo), Chemic
Al Reviews, 91, 165-195, 1991.
In the present invention, R ₁ and R ₂ are defined by σ _p values, but this does not mean that the values known in the literature described in these publications are limited to certain substituents, and the values are unknown in the literature. However, as a matter of course, it is included as long as it is included in the range when measured based on the Hammett's rule.

Specific examples of R ₁ and R ₂ which are electron withdrawing groups having a σ _p value of 0.2 or more and 1.00 or less include an acyl group, an acyloxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group and cyano. Group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group,
Sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl group substituted with at least two or more halogen atoms, alkoxy group substituted with at least two or more halogen atoms, aryl substituted with at least two or more halogen atoms Oxy group, alkylamino group substituted with at least two or more halogen atoms, alkylthio group substituted with at least two or more halogen atoms, aryl group substituted with another electron-withdrawing group having a σ _p value of 0.2 or more , A heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group. Among these substituents, the group which can have further substitution may further have a ring-substituting group as mentioned later for R ₃ .

The aliphatic oxycarbonyl group is an aliphatic moiety whose aliphatic moiety may be linear, branched or cyclic and which may contain a saturated or unsaturated bond.
An aliphatic oxycarbonyl group is an alkoxycarbonyl,
It includes cycloalkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkenyloxycarbonyl and the like. Hereinafter, the term "aliphatic" is used synonymously with the above.

[0044] When the typical sigma _p value is listed sigma _p value of the electron withdrawing groups 0.2 to 1.0, a bromine atom (0.23), chlorine atom (0.23), a cyano group (0.66), nitro group (0.78) ,
Trifluoromethyl group (0.54), tribromomethyl group (0.29), trichloromethyl group (0.33) carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.4
3), acetyloxy group (0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72),
Benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy Group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred examples of the substituent of R ₁ are a cyano group and an aliphatic oxycarbonyl group (an aliphatic oxycarbonyl group having a carbon number of 36 or less, such as methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl). , 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl,
Oleyloxycarbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, 2,
6-di-t-butyl-4-methylcyclohexyloxycarbonyl), a dialkylphosphono group (a dialkylphosphono group having a carbon number of 36 or less, such as dimethylphosphono, diethylphosphono, an alkyl or arylsulfonyl group ( An alkyl or arylsulfonyl group having 36 or less carbon atoms, such as a methanesulfonyl group, a butanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group), a fluorinated alkyl group (a fluorinated alkyl group having 36 or less carbon atoms) , For example, trifluoromethyl .. The substituent of R ₁ is particularly preferably a cyano group, an aliphatic oxycarbonyl group or a fluorinated alkyl group, and most preferably a cyano group.

As an example of the substituent of R ₂ , preferably R ₁
Such as the aliphatic oxycarbonyl group, the carbamoyl group (carbamoyl group having 36 or less carbon atoms, for example, diethylcarbamoyl, dioctylcarbamoyl), the sulfamoyl group (sulfamoyl group having 36 or less carbon atoms, for example, dimethylsulfamoyl group) , Dibutylsulfamoyl), a dialkylphosphono group and a diarylphosphono group as described above for R ₁ (a diarylphosphono group having a carbon number of 48 or less, and examples thereof include diphenylphosphono and di (p-toluylphosphono)). The substituent of R ₂ is particularly preferably an aliphatic oxycarbonyl group represented by the following general formula (4).

[0047]

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In the formula, R ₁ 'and R ₂ ' represent an aliphatic group having 36 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl,
Represents tridecyl, cyclopentyl, cyclohexyl.
R ₃ ′, R ₄ ′ and R ₅ ′ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups mentioned above for R ₁ 'R ₂ '. R ₃ ′, R ₄ ′ and R ₅ ′ are preferably a hydrogen atom.

Z represents a group of non-metal atoms necessary for forming a 5- to 8-membered ring, and this ring may be substituted, may be a saturated ring or may have an unsaturated bond. good. The non-metallic atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a piperazine ring, an oxane ring and a thian ring, and these rings are R ₃ described later.
It may be substituted with a substituent represented by. The ring formed by Z is preferably an optionally substituted cyclohexane ring, and particularly preferably the 4-position has 24 carbon atoms.
A cyclohexane ring substituted with the following alkyl group (which may be substituted with a substituent represented by R ₃ described later).

R in the general formulas (2-1) to (2-5)
₃ represents a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an aliphatic group (preferably an aliphatic group having 36 or less carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, t-amyl, t
-Octyl, tridecyl, cyclopentyl, cyclohexyl), an aryl group (preferably an aryl group having 36 or less carbon atoms, for example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably 36 or less carbon atoms, 5
To 8-membered heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl) , A cyano group, a hydroxyl group, a nitro group, a carboxyl group, a sulfo group, an aliphatic oxy group (preferably an aliphatic oxy group having a carbon number of 36 or less,
For example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 36 or less carbon atoms, for example, Phenoxy, 2-naphthoxy), heterocyclic oxy group (preferably a heterocyclic oxy group having 36 or less carbon atoms, for example, 1-phenyltetrazole
-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy),

Acylamino group (preferably an acylamino group having a carbon number of 36 or less, for example, acetamide, benzamide), amino group (preferably an amino group having a carbon number of 36 or less, for example, amino, methylamino, N, N-diethylamino) , N, N-dioctadecylamino), anilino group (preferably anilino group having 36 or less carbon atoms, for example, anilino, N-methylanilino), heterocyclic amino group (preferably heterocyclic amino group having 36 or less carbon atoms) ,
For example, a 4-pyridylamino group, a ureido group (preferably a ureido group having 36 or less carbon atoms, for example, N—N dimethylureido, N-phenylureido), a sulfamoylamino group (preferably a ureido group having 10 or less carbon atoms). A famoylamino group, for example, N, N-dipropylsulfamoylamino, N-ethylsulfamoylamino), an aliphatic thio group (preferably an aliphatic thio group having a carbon number of 36 or less, for example, methylthio, ethylthio ), An arylthio group (preferably an arylthio group having 36 or less carbon atoms, for example, phenylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 36 or less carbon atoms, for example, 2-benzothiazolylthio, 2- Pyridylthio, 1-phenyltetrazolylthio),

Aliphatic oxycarbonylamino group (preferably aliphatic oxycarbonylamino group having 36 or less carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino), aryloxycarbonylamino group (preferably 36 carbons
In the following aryloxycarbonylamino group, for example,
A phenoxycarbonylamino group), a sulfonamide group (preferably a sulfonamide group having 36 or less carbon atoms, such as methanesulfonamide, ethanesulfonamide,
Benzenesulfonamide), carbamoyl group (C3
A carbamoyl group of 6 or less, for example, carbamoyl,
N, N-dimethylcarbamoyl, N-propylcarbamoyl), a sulfamoyl group (preferably a sulfamoyl group having a carbon number of 36 or less, for example, sulfamoyl, N,
N-dimethylsulfamoyl, N-ethylsulfamoyl, N-phenylsulfamoyl), sulfonyl group (preferably an alkyl or arylsulfonyl group having 36 or less carbon atoms, for example, methanesulfonyl, benzenesulfonyl), aliphatic oxy Carbonyl group (preferably an alkoxycarbonyl group having a carbon number of 36 or less, for example, ethoxycarbonyl, t-butoxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having a carbon number of 36 or less, for example, Phenoxycarbonyl), an azo group (preferably an azo group having a carbon number of 36 or less, for example, phenylazo),

Acyloxy group (preferably an acyloxy group having a carbon number of 36 or less, for example, acetoxy, pivaloyloxy, benzoyloxy), carbamoyloxy group (preferably a carbamoyloxy group having a carbon number of 36 or less, for example, N, N-dimethyl Carbamoyloxy, N
-Butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having a carbon number of 36 or less, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), a silyloxy group ( Preferably, it is a silyloxy group having 36 or less carbon atoms,
For example, trimethylsilyloxy, t-butyldimethylsilyloxy, triphenylsilyloxy), an imide group (preferably an imide group having 36 or less carbon atoms, for example, N
-Succinimide group, N-phthalimide), sulfinyl group (preferably alkylsulfinyl group or arylsulfinyl group having 36 or less carbon atoms, for example, butanesulfinyl, benzenesulfinyl), phosphonyl group (preferably phosphonyl group having 36 or less carbon atoms) , For example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), and an acyl group (preferably an acyl group having a carbon number of 36 or less, for example, formyl, acetyl, pivaloyl, benzoyl).

These substituents may further have a substituent, and a preferable substituent is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, Sulfo group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, acylamino group, amino group, anilino group, heterocyclic amino group,
Ureido group, sulfamoylamino group, aliphatic thio group,
Arylthio group, heterocyclic thio group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group,
Examples include sulfonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, azo group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, silyloxy group, imide group, sulfinyl group, phosphonyl group, acyl group and azolyl group. .

General formulas (2-1), (2-2) and (2-
In 4), X represents a hydrogen atom or a group capable of splitting off upon coupling with the oxidation product of the color developing agent (hereinafter, simply referred to as splitting group). When X represents a leaving group, the leaving group may be a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy), aryloxy (eg, phenoxy, 4-chloro). Phenoxy, 4-carboxyphenoxy, naphthyloxy), heterocyclic oxy group (for example, 5-
Phenyltetrazolyloxy, 2-benzothiazolyloxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl, aryl, or heterocyclic sulfonyloxy group (for example,
Methanesulfonyloxy, benzenesulfonyloxy), dialkyl or diarylphosphonooxy groups (eg, dimethylphosphonooxy, diphenylphosphonooxy), dialkyl or diarylphosphinooxy groups (eg, dimethylphosphinooxy),

Alkyl, aryl, or heterocyclic sulfonyl groups (eg, methanesulfonyl, toluenesulfonyl, tetrazolylsulfonyl), alkyl, aryl, or heterocyclic sulfinyl groups (eg, phenyl, phenyl, ethylsulfinyl, tetrazolylsulfinyl) ), An acylamino group (for example, dichloroacetylamino, heptafluorobutylamino), an alkyl,
Aryl or heterocyclic sulfonamide (eg, methanesulfonamide, trifluoromethanesulfonamide, benzenesulfonamide), alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy), aryloxycarbonyloxy group (eg, phenoxycarbonyl) Oxy), carbamoyloxy group (diethylcarbamoioxy, morphocarbonyloxy), alkyl, aryl, or heterocyclic thio group (eg, ethylthio, phenylthio, tetrazolylthio), carbamoylamino group (eg, N-
Methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom (for example, imidazolyl,
Pyrazolyl, triazolyl, tetrazolyl), imide group (for example, succinimide, phthalimide), arylazo group (for example, phenylazo). X is preferably a hydrogen atom.

In the general formulas (2-3) and (2-5), G represents a hydrogen atom or a blocking group which can be split off by hydrolysis during a photographic process or an intramolecular nucleophilic substitution reaction. Typical examples of the Broking group which can be eliminated by hydrolysis include U.S. Pat. Nos. 2,575,182, 2,706,685, and 2,706,685.
Examples include those described in Nos. 2865748 and 4123281. Further, as a representative example of the Broking group which can be eliminated by an intramolecular nucleophilic substitution reaction, those described in JP-A-55-53330 can be mentioned. G is preferably a hydrogen atom.

Preferred embodiments of the coupler of the present invention can be represented by the following general formulas (5) and (6). (More preferably, R ₁ = cyano group, R ₂ = aliphatic group, R ₃ = aryl group or aliphatic group). A coupler represented by the general formula (5) is particularly preferable.

[0059]

[Chemical 12]

In the general formulas (5) and (6), R ₁ to
R ₇ and n ₁ have the same meanings as described above. Next, specific compound examples of the present invention will be given, but the present invention is not limited thereto.

[0061]

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[0062]

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[0063]

[Chemical 15]

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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Next, specific synthesis examples of the compound of the present invention will be described. Compound Example 12 was synthesized according to the following scheme.

[0070]

[Chemical 21]

Synthesis of Compound b Pyrrolotriazole coupler a (50 g) obtained by the method described in JP-A-5-202004, methoxyethoxymethyl chloride (14.8 g), and potassium carbonate (16.4 g)
Was stirred in dimethylacetamide (300 ml) at 50 ° C for 30 minutes. After cooling the reaction solution to room temperature, ethyl acetate /
It was added to diluted hydrochloric acid water. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was recrystallized from ethyl acetate / hexane to obtain compound b (46 g).

Synthesis of Compound c Boron tribromide (15.6 ml) was added dropwise to a solution of compound b (46 g) in dichloromethane (460 ml) at 0 ° C.
Stir for minutes. The reaction solution was poured into ethyl acetate / dilute hydrochloric acid. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was recrystallized from ethyl acetate / hexane to give compound c (34
g) was obtained.

Synthesis of Exemplified Compound 12 To a solution of naphthol derivative d (9 g) in dimethylacetamide (250 ml) was added 60% sodium hydride (3.24 g) at 0 ° C. under a nitrogen stream, and the mixture was stirred for 15 minutes. Compound c (24.3 g) was slowly added to this solution at 0 ° C., and the mixture was further stirred for 15 minutes. The reaction solution was poured into ethyl acetate / dilute hydrochloric acid. The organic layer was washed with water and brine and then dried over anhydrous sodium sulfate. Exemplified compound 1 was obtained by concentrating under reduced pressure and recrystallizing the residue from ethyl acetate / hexane.
2 was obtained (22 g).

The light-sensitive material of the present invention may have at least one layer containing the coupler of the present invention on a support,
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general light-sensitive material can be constituted by coating a support with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in this order. However, the order may be different from this. An infrared-sensitive silver halide emulsion layer can also be used in place of at least one of the above-mentioned photosensitive emulsion layers. Color reproduction of the subtractive method is performed by incorporating a silver halide emulsion having sensitivity in each wavelength range and a color coupler forming a dye having a complementary color relationship with the light to be exposed in these light-sensitive emulsion layers. be able to. However, the photosensitive emulsion layer and the coloring hue of the color coupler may not have the above correspondence. In the present invention, it is particularly preferable to use a cyan coupler in a red-sensitive silver halide emulsion layer. The content of the coupler of the present invention in the light-sensitive material is appropriately 1 × 10 ⁻³ mol to 1 mol, preferably 2 × 10 ⁻³ mol to 3 × 10 1 mol per mol of silver halide in the same layer. ^-1 mole.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (if necessary, a low-boiling organic solvent is also used), and is emulsified and dispersed in a gelatin aqueous solution to be halogenated. The oil-in-water dispersion method of adding to a silver emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , The same 2,541,23
No. 0, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 0.
No. 29104, etc., and the dispersion with an organic solvent-soluble polymer is described in PCT International Publication No. WO88.
/ 00723.

As the high boiling point organic solvent which can be used in the above oil-in-water dispersion method, phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis ( 2,4-di-tert
-Amylphenyl) isophthalate, bis (1,1-di-ethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-) Dichlorobenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyl dodecane amide, N, N-diethyl lauryl amide), alcohols or phenols (isos 1 allyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (eg, dibutoxyethyl succinate) , Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert. -Octylaniline, etc.),
Chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-te)
rt-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-
(4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert)
-Amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid), JP-A-6-258
Examples thereof include sulfonamide compounds described in 803 and European Patent EP606659A. These high boiling point organic solvents may be used alone or in combination of two or more. The boiling point of the auxiliary solvent is 3
An organic solvent having a temperature of 0 ° C. or higher and about 160 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The high-boiling organic solvent can be used in an amount of 0 to 10.0 times, preferably 0 to 5.0 times, and more preferably 0.5 to 4.5 times the weight ratio of the coupler.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and the processing method and processing addition applied for processing the light-sensitive material. European Patent EP
0,355,660A2, JP-A-5-34889,
4-359249, 4-317375, 4-
No. 270344, No. 5-66527, No. 4-3454
No. 8, No. 4-145433, No. 2-854, No. 1-
Nos. 158431, 2-90145 and 3-1945
Nos. 39, 2-93641, 6-43611, 6-3779, 6-208196, 6-118
546, European Patent EP 0520457A2, Resear
ch Disclosure No. 37038 (1995) and the like, and a silver halide color photographic light-sensitive material and its processing method are also preferable.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer composition Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan that can be used in combination Page 149, line 29 to line 33; European Patent 432 Coupler, 804A2, page 3, line 28 to page 40 2 Line 6) Polymer coupler, page 149, lines 34 to 38; European Patent 435,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler, page 53, line 42 to line Page 137, line 34, page 149, line 39 -Line 45 to 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; European Patent 435,334A3, 3rd line Page 1, line 1 to page 29, line 50 9) Antiseptic and antifungal agent Page 150, line 25 to line 28 10) Formalin scabé Page 149, line 15 to line 17 Nanger 11) Other additives Pp. 153, line 38-47; European Patent No. 421,453A1, page 75, line 21-page 84, line 56, page 27, line 40-page 37, line 40 12) Dispersion method Method page 150, lines 4 to 24 13) Support material, page 150, lines 32 to 34 14) Film thickness and film physical properties, page 150, lines 35 to 49 15) Color development / black and white development Page 150, line 50 to page 151, line 47; European special / fog process page 442, 323A2, page 34 Lines 11 to 54, page 35, lines 14 to 22 16) Desilvering process page 151, line 48 to page 152, line 53 17) Automatic developing machine page 152, line 54 to Page 153, line 2 18) Washing / stabilization process Page 153, line 3 to line 37

[0081]

【Example】

(Embodiment 1) Hereinafter, the present invention will be described in detail with reference to embodiments, but is not limited thereto. Preparation of Sample 101 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: antihalation layer Black colloidal silver 0.10 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 0.10 g of a microcrystalline solid dispersion of Dye E-1

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling point organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third Layer: Intermediate Layer Finely grained silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.050 g yellow colloidal silver silver amount 0.030 g gelatin 0.40g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.40 g Emulsion B Silver amount 0.25 g Gelatin 0.80 g Coupler C-1 0.15 g Coupler C-2 0.10 g Coupler C-9 0.010 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.05 g High boiling point organic solvent Oil-1 0.05 g Additive P-1 0.10 g

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.25 g Emulsion C Silver amount 0.35 g Gelatin 0.80 g Coupler C-1 0.05 g Coupler C-2 0.05 g Coupler C-3 0.05 g High boiling point organic solvent Oil-2 0.05g High boiling point organic solvent Oil-1 0.05g Additive P-1 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.10 g Coupler C-2 0.10 g Coupler C-3 0.50 g Additive P-1 0.10 g

Seventh layer: Intermediate layer Gelatin 0.70 g Additive M-1 0.30 g Compound Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 10.0 mg High boiling organic solvent Oil-1 0.020 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.020 g Yellow colloidal silver Silver amount 0.020 g Gelatin 1.00g Additive P-1 0.05g Color mixing inhibitor Cpd-A 0.10g High boiling organic solvent Oil-3 0.10g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.20 g Emulsion F Silver amount 0.20 g Emulsion G Silver amount 0.10 g Gelatin 0.50 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.10 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.10 g High boiling point organic solvent Oil-2 0.10g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.25 g Emulsion H Silver amount 0.10 g Gelatin 0.60 g Coupler C-4 0.070 g Coupler C-7 0.050 g Coupler C-8 0.070 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g High boiling point organic solvent Oil-2 0.050 g

Eleventh layer: High sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.35 g Gelatin 1.00 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg High boiling point organic solvent Oil-1 0.050 g High boiling point organic solvent Oil-2 0.020 g

Twelfth layer: intermediate layer Gelatin 0.60 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.010 g Gelatin 1.10 g Color mixture inhibitor Cpd-A 0.10 g High boiling point organic solvent Oil-3 0.05 g Dye E-2 microcrystalline solid dispersion 0.030 g Dye E-3 microcrystalline solid dispersion 0.020 g

Layer 14: Intermediate layer Gelatin 0.60 g Layer 15: Low sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.40 g Compound Cpd-I 0.02 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10g

[0098]

Layer 19: Second protective layer Colloidal silver Silver amount 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.40 g

20th layer: 3rd protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.10 g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

[Chemical formula 26]

[0110]

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[0111]

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[0112]

[Chemical 29]

[0113]

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[0114]

[Chemical 31]

[0115]

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[0116]

[Chemical 33]

[0117]

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[0118]

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Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
A peripheral speed of about 10 m / sec through the slurry and a discharge rate of 0.51
/ Min for 8 hours. The beads were removed by filtration and diluted with water to a dye concentration of 3% by adding water.
Heated at ° C for 10 hours. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (standard deviation of particle size × 100 / average particle size) was 18%.

Similarly, solid dispersions of Dyes E-2 and E-3 were obtained. Average particle size 0.54μm and 0.56μ
It was m.

C added to the fourth to sixth layers of sample 101
Samples 102 to 110 were prepared in the same manner except that -1, 2, and 3 were changed as shown in Table 4. The addition amount of the pyrroloazole coupler in each layer was unified to 45 mol% of the total coupler amount of C-1, 2, and 3 in each layer of Sample 101. The intermediate layer A is between the fourth layer and the fifth layer, and the intermediate layer B is
Is applied between the fifth layer and the sixth layer, and the constitutions of the intermediate layers A and B are as follows.

Intermediate layer A or B Gelatin 0.40 g High boiling point organic solvent Oil-1 0.10 g Compound Cpd-A 0.05 g (however, a surfactant was used as in the other layers)

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[Table 4]

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(Evaluation of Color Reproducibility) A color checker chart manufactured by Macbeth was photographed using Samples 101 to 110 to evaluate color reproducibility. When shooting, the color balance is adjusted using a color filter for each sample, and the evaluation is performed by 5 people who are involved in image evaluation at Fuji Photo Film Co., Ltd. Ashigara Research Laboratory. Green and blue are limited to 5 points per person. The one with high turbidity and low saturation of the issue green was scored as a high score and evaluated with the total score. (Measurement of Sensitivity) Samples 101 to 110 are exposed to white light having a color temperature of 4800 degrees through a wedge whose density is continuously changed, and then subjected to the development processing described below to give a cyan density of 1.0. The sensitivity S _{R1.0 of} was measured. Comparative sample 1
The S _{R1.0 of} 01 was compared with other samples, and the direction with higher sensitivity is shown in Table 5 as a positive value. (Evaluation of Sharpness) Samples 101 to 110 were exposed to white light through an MTF pattern and subjected to the processing described below, and then the MTF value of a cyan image (10 cycles / m).
m) was measured and the sharpness was compared. The evaluation was performed by the ratio (MTF ratio) when the MTF value of Sample 101 was 1.0. The above results are summarized in Table 5.

[0126]

[Table 5]

As shown in Table 5, in Samples 102 to 110 in which the pyrroloazole coupler was used, in Sample 101 in which the phenol cyan coupler was used, in Green,
The reproducibility of blueish green is improved. Samples 102 and 103 have lower sensitivity than sample 101, but the sample containing the coupler of the present invention does not lower sensitivity and is excellent in sharpness. Samples 102 and 10
3, the samples using the coupler of the present invention are excellent in sharpness as compared with the samples 107 and 108 in which the intermediate layers A and B are provided to improve the sensitivity.

In the present embodiment, the following development processing was performed. In processing, 50% of the sample 101 was completely exposed to white light, and was used after passing until the replenishment amount became three times the tank capacity. Processing time Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 12 liters 2200 ml / m ² Second water wash 2 minutes 38 ° C 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C 4 liters 1100 ml / m ² Developing 6 minutes 38 ° C 12 liters 2200 ml / m ² Pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² Bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² Fixed 4 minutes 38 ° C 8 liters 1100 ml / m ² Second washing 4 minutes 38 ° C 8 liters 7500 ml / m ² Final rinse 1 minute 25 ° C 2 liters 1100 ml / m ²

The composition of each processing solution was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Potassium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 mL 1000 mL pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal Liquid] [Tank Liquid] [Replenishing Liquid] Nitrilo-N, N, N-trimethylenephosphonic acid Tank Liquid ・ Same as 3.0 g of sodium salt Stannous chloride ・ dihydrate 1.0 g p-amino Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 7.0 g 7.0 g trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline ・ 3/2 sulfuric acid ・ monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water to add 1000 ml 1000 ml pH 11.80 12.00 Adjust the pH with sulfuric acid or potassium hydroxide. did.

[Pre-bleaching] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 8.0 g 8.0 g sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g formaldehyde sodium bisulfite adduct 30 g 35 g Water was added to 1000 ml 1000 ml pH 6.30 6.10 The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenishing solution] Ethylenediamine tetraacetic acid / sodium salt / dihydrate 2.0 g 4.0 g Ethylenediamine tetraacetic acid / Fe (III) / ammonium / dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing liquid] [Tank liquid] [Replenishing liquid] Ammonium thiosulfate 80 g The same sodium sulfite 5.0 g 〃 sodium bisulfite 5.0 g 〃 water is added to the tank liquid 1000 ml 〃 pH 6.60 It was adjusted.

[Stabilizing liquid] [Tank liquid] [Replenishing liquid] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g polymalein Acid (average molecular weight 2,000) 0.1 g 0.15 g Add water 1000 ml 1000 ml pH 7.0 7.0

Example-2 1) Support The support used in this example was prepared by the following method. 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber were dried by a conventional method and then melted at 300 ° C. Then, it was extruded from a T-die and stretched longitudinally at a stretch ratio of 3.0 at 140 ° C.
Then, the film was transversely stretched 3.0 times, and heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm to give a heat history at 110 ° C. for 48 hours. 2) Coating of undercoat layer The support is subjected to a corona discharge treatment, a UV discharge treatment, a glow discharge treatment, and a flame treatment on both surfaces thereof.
An undercoat solution having the following composition was applied to each surface, and an undercoat layer was provided on the high-temperature side during stretching. Corona discharge treatment is pillar Pill
A 30 cm wide support is treated at 20 m / min using a solid state corona treatment machine 6KVA model manufactured by ar. At this time,
From the current and voltage readings, the processed object is 0.375 KV
And processing of A · min / m ² was made. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. UV discharge treatment is 75
Discharge treatment was performed while heating at ℃. Further, in the glow discharge treatment, irradiation was performed with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 ml Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g formaldehyde 0.02 g salicylic acid 0.1 g diacetyl cellulose 0.5 g p-chlorophenol 0.5 g resorcin 0.5 g cresol 0 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g Aziridine 3 times molar adduct of trimethylolpropane 0.2 g 3 times molar adduct of trimethylolpropane-toluene diisocyanate 0.2 g methanol 15 ml acetone 85 ml formaldehyde 0.01 g acetic acid 0.01 g concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer, a magnetic recording layer and a sliding layer having the following compositions were coated as back layers. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight were dissolved in 3000 parts by weight of ethanol to obtain a homogeneous solution. To this solution, a 1N aqueous solution of sodium hydroxide was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, the precipitate was added with water and washed by centrifugation. This operation was repeated three times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions were removed were redispersed in 1500 parts by weight of water,
The mixture was sprayed into a baking furnace heated to ℃ to obtain fine tin powder of tin oxide-antimony oxide composite having a bluish average particle diameter of 0.005 μm. The specific resistance of the fine particle powder was 5Ω · cm. A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and after coarse dispersion with a stirrer, a horizontal sand mill (trade name: Dynomill; WILLYA.BA)
(CHOFENAG) until the residence time became 30 minutes. At this time, the average particle size of the secondary aggregate was about 0.04 μm.

3-1-2) Coating of Conductive Layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-chlorophenol 0.5 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The obtained conductive film had a resistance of 10 ^8.0 (100 V), and had excellent antistatic performance. 3-2) Coating of magnetic recording layer Magnetic substance Co-coated γ-Fe ₂ O ₃ (major axis 0.14 μm, single axis 0.1 μm)
Needle-shaped 03μm, specific surface area 41m ² / g, saturation magnetization 89em
u / g, the surfaces of which are aluminum oxide and silicon oxide, each of which is surface-treated with 2% by weight of Fe ₂ O _3. Coercive force 930 Oe, Fe ⁺²
1/100 g of a (/ Fe ⁺³ ratio of 6/94) was added to 220 g of water and 150 g of a silane coupling agent of poly (polymerization degree 16) oxyethylenepropyltrimethoxysilane, and kneaded well in an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. overnight to remove water,
Magnetic particles subjected to surface treatment by heating at 110 ° C. for 1 hour were produced. Further, the mixture was kneaded again with an open kneader according to the following formulation.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Further, diacetyl cellulose and trimethylolpropane-toluene diisocyanate as a curing agent in a three-fold molar amount were added to the binder at 20 wt%. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone such that the viscosity of the liquid was about 80 CP. Also, the application is
1.2μm thickness on the above conductive layer with a bar coater
I went to. The coating was performed such that the amount of the magnetic material was 62 mg / m ² . Silica particles (0.3
μm) and an abrasive aluminum oxide (0.5 μm) were added so as to be 10 mg / m ² . Drying is 115 ° C, 6
(All rollers and transporting devices in the drying zone are at 115 ° C.). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer is 4.2 emu / m ² , the coercive force is 923 Oe,
The squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following formulation liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b) 9 mg / m ^{2 The} compound a / compound b (6: 9) was composed of xylene and propylene glycol monomethyl ether (volume ratio 1:
1) Heat and dissolve in a solvent at 105 ° C., and dissolve this solution in a 10-fold amount of propylene glycol monomethyl ether (25
C.) to give a fine dispersion. After further diluting in a 5-fold volume of acetone, the mixture was redispersed with a high-pressure homogenizer (200 atm) to obtain a dispersion (average particle size: 0.01 μm) and then used. The performance of the obtained sliding layer was as follows: a dynamic friction coefficient of 0.06 (a stainless steel hard ball of 5 mmφ, a load of 100
g, speed 6 cm / minute), static friction coefficient 0.07 (clip method), and excellent characteristics. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of Sensitive Material Layer Next, on the side opposite to the back layer obtained above, Example-1
Each of the same layers as those of Samples 101 to 110 of No. 1 were applied in multiple layers to form Samples 201 to 210, respectively.

When samples 201 to 210 were exposed and developed in the same manner as in Example-1, good results were obtained as in Example-1.

(Example-3) Sample 301, which is a multilayer color light-sensitive material, was obtained by applying multiple layers of the following composition on a cellulose triacetate film support having an undercoat.
Was produced. (Photosensitive layer composition) The main materials used are classified as follows; ExC: Cyan coupler UV: Ultraviolet absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 301) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion Em-1 silver 0.30 silver iodobromide emulsion Em-2 silver 0.20 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Comp-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion Em-3 Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC- 1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Comp-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Em-4 silver 1.60 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC- 1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Comp-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Comp-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Em-5 silver 0.15 Silver iodobromide emulsion Em-6 silver 0.10 Silver iodobromide emulsion Em-7 silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 x 10 ^-4 ExS-6 8.0 x 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion Em-8 Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC- 8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Em-9 silver 1.30 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC- 1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Comp-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Comp-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Em-9 Silver 0.10 Silver iodobromide emulsion Em-10 Silver 0.05 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Comp-2 0.10 Comp-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Em-11 Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Comp-2 0.10 Comp- 3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion Em-13 Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B- 3 0.05 Comp-4 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coatability of each layer, WS-1 to WS-6, B-3 to B-
6, FS-1 to FS-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0160]

[Table 6]

In Table 6, (1) Emulsions Em-10 to Em-12 were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions Em-1 to Em-9 were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It is sensitized. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion Em-12 is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

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[Chemical 40]

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[Chemical 51]

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The third of the sample 101 prepared as described above,
Samples 302 to 307 were prepared in the same manner except that the cyan couplers ExC-1 and 4 of the four and five layers were changed as shown in Table-7. The addition amount of the pyrroloazole coupler in each layer was unified to 50% of the total number of moles of ExC-1 and 4 before the change.

[0181]

[Table 7]

Samples 301 to 307 were MT with white light.
Exposure is given through the F pattern, and
After performing the developing treatment described in No. 10, the MTF value (10 cycles / mm) of the cyan image was measured and the sharpness was compared.
The evaluation was performed with a ratio (MTF ratio) when the MTF value of Sample 301 was 1.0, and as a result, the sample of the present invention was excellent in sharpness.

Claims (1)

[Claims] 1. A silver halide color light-sensitive material characterized in that at least one layer on a support contains a coupler represented by the following general formula (1). General formula (1) In the general formula (1), Cp ₁ represents a coupler residue capable of reacting with an oxidized product of a color developing agent to form a dye flowing out from the photographic light-sensitive material during processing. T represents a linking group which is released from Cp ₁ by coupling between Cp ₁ and an oxidized color developing agent and can subsequently release the Cp ₂ portion, and n represents 0 or 1. Cp ₂ represents a coupler residue represented by the following general formula. Embedded image R ₁ and R ₂ in the general formulas (2-1) to (2-5)
Respectively have Hammett's substituent constant σ _p values of 0.2 or more 1.
It represents an electron-withdrawing group of 0 or less, and R ₃ represents a substituent. In the general formulas (2-1), (2-2) and (2-4), X represents a hydrogen atom or a group capable of splitting off upon coupling with the oxidation product of the color developing agent. General formula (2-3), (2-
In 5), G represents a hydrogen atom or a blocking group which can be removed by hydrolysis during the photographic process or an intramolecular nucleophilic substitution reaction.