JP2640149B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a multilayer silver halide color light-sensitive material, and more particularly to a multilayer halogen containing a combination of novel couplers having good coloring properties and suitable for rapid processing. It relates to a silver halide color light-sensitive material (hereinafter referred to as a light-sensitive material).

(Background Art) In a silver halide color light-sensitive material, a photosensitive layer composed of three kinds of silver halide emulsion layers selectively spectrally sensitized is coated on a support in a multilayer structure. For example, a so-called color printing paper (hereinafter referred to as a color paper) is provided with a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer in this order from the side to which light is normally exposed. Are provided with an intermediate layer, a protective layer, and the like, which prevent color mixing and absorb ultraviolet rays.

In general, in a so-called color positive film, a green-sensitive emulsion layer, a red-sensitive emulsion layer, and a blue-sensitive emulsion layer are coated in this order from the side far from the support, that is, from the side to be exposed. In a color negative film, the layer arrangement is diversified, and it is general that a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are coated in this order from the exposed side. In a light-sensitive material having two or more different emulsion layers, light-sensitive materials in which emulsion layers having different color sensitivity are arranged between the emulsion layers are scattered, and a yellow filter layer, an intermediate layer, a protective layer and the like capable of bleaching are provided. Inserted.

In order to form a color photographic image, photographic couplers of three colors, yellow, magenta and cyan, are contained in a photosensitive layer, and the exposed photosensitive material is subjected to color development processing using a so-called color developing agent. An oxidized form of an aromatic primary amine undergoes a coupling reaction with a coupler to give a chromophore, but the coupling speed at this time is as large as possible, and a high color density is provided within a limited development time. Those having good coloring properties are preferred. Furthermore, coloring pigments
All of them are vivid cyan, magenta, and yellow dyes with little side absorption and are required to provide color photographic images with good color reproducibility.

(Problems to be Solved by the Invention) The conventional light-sensitive materials, particularly in color paper, have insufficient coloring properties of yellow couplers compared to magenta couplers and cyan couplers, and are particularly suitable for high-temperature rapid processing which has recently become popular. This is a serious problem.

In order to obtain good image quality, it is required that yellow, magenta, and cyan densities can be obtained within a certain development processing time, and that the color balance does not vary much. Therefore, a new combination of couplers having good coloring properties is demanded.

In order to partially solve such problems, combinations of various couplers, especially yellow, magenta and cyan couplers, have been proposed.

For example, JP-A Nos. 62-165656, 57-200037, 59
No. 57238, No. 60-205446, No. 61-4047, U.S. Pat.No. 4,607,002, JP-A No. 62-166339, 62-173464
Nos. 63-167361, U.S. Pat.Nos. 4,748,100 and 4,62
No. 2,287, JP-A-60-222852 and JP-A-61-50136 describe examples.

However, in the combination of these couplers, the color development of the yellow coupler is insufficient, and the color balance of cyan, magenta, and squid fluctuates, and the combination has not been completely solved.

The present invention is intended to solve the above problems at the same time, and more specifically, an object of the present invention is to provide a multi-layer halogen having a good coloring property, and particularly, a color balance which does not fluctuate even in high-temperature rapid processing. An object of the present invention is to provide a silver halide color photographic material.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least three kinds of light-sensitive layers having different color sensitivities on a support, The second photosensitive layer contains at least one kind of coupler represented by the following formula (II), and the third photosensitive layer contains at least one kind of coupler represented by the following formula (II). At least one of the couplers represented by (III)
This has been effectively achieved by a silver halide color photographic material characterized by containing a seed.

General formula (I) (Wherein, R ₁₁ represents an alkyl group or an aryl group;
₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group, R ₁₃ represents an alkyl group, an aryl group or a heterocyclic group, and J ₁₁ represents -SO ₂ -or Represents a group represented by, J ₁₂ is -SO _2- , Or -CO ₂ - represents a group represented by, Z ₁₁ represents a group or atom capable of splitting off upon reaction with an oxidation product of hydrogen atoms or an aromatic primary amine developing agent. ) General formula (II) (Wherein, R ₂₁ represents a hydrogen atom or a substitutable group;
₂₁ represents a hydrogen atom or a group or atom which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent. However, R ₂₁ and Z ₂₁ do not simultaneously represent a hydrogen atom. Z ₂₂ , Z ₂₃ and Z ₂₄ are each -N = or represents -NH-, Z ₂₄ -Z ₂₃ bond and Z ₂₃ -Z ₂₂
One of the bonds is a double bond and the other is a single bond. The case where Z ₂₃ -Z ₂₂ is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. ) General formula (III) (Wherein, R ₃₁ represents an alkyl group, an aryl group, an amino group or a heterocyclic group, R ₃₂ represents an acylamino group or an alkyl group, and R ₃₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amide group. And R ₃₂ and R
₃₃ may combine to form a 5- to 7-membered ring. Z ₃₁ represents a hydrogen atom or a group or atom which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent. ) In the present specification, an alkyl group (alkyl residue),
An aryl group (aryl residue), an amino group (amino residue), a heterocyclic group or a heterocyclic group (these residues),
A sulfonyl group (sulfonyl residue), a sulfinyl group and the like are used in a meaning including those further substituted with a substituent.

 The general formula (I) will be described in detail.

In formula (I), the alkyl group represented by R ₁₁ include unsubstituted alkyl groups and substituted alkyl groups, the alkyl groups such as methyl, ethyl, propyl, butyl, t-
Butyl, sec-butyl and the like. Examples of the substituent that can be introduced into the alkyl group include a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkoxy group (eg, methoxy, ethoxy), an aryloxy group (eg, phenoxy, 2,4-di-t-amylphenoxy, -Chlorophenoxy), an alkylthio group (eg, phenylthio), an alkylsulfonyl group (eg, a methanesulfonyl group), an arylsulfonyl group (eg, benzenesulfonyl), an acylamino group (eg, acetylamino), an amino group (eg, diethylamino), a cyano group, and the like. No.

The aryl group represented by R ₁₁ is preferably a phenyl group, and may have a substituent. Examples of the substituent of the aryl group include the same groups as those of the alkyl group. In addition, the alkyl group (for example, methyl, ethyl, t-
Butyl group).

R ₁₂ represents a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom) or an alkoxy group (eg, methoxy, ethoxy, butoxy, hexyloxy, dodecyloxy, tetradodecyloxy, hexadecyloxy).

The alkyl group represented by R ₁₃ includes an unsubstituted alkyl group and a substituted alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, 2-ethylhexyl, decyl, tetradecyl, pentadecyl, i-pentadecyl, heptadecyl, and i-heptadecyl. Examples of the substituent that can be introduced into the alkyl group include the aforementioned
The substituents represented by R ₁₁ are exemplified.

The aryl group represented by R ₁₃ is preferably a phenyl group, and may have a substituent. Besides sulfonamide group substituents as the substituent of the aryl group represented as substituents of the alkyl group and the aryl group in said R ₁₁ (e.g., methanesulfonamido, tetradecane sulfonamido), an alkoxycarbonyl group (e.g. methoxycarbonyl, Decyloxycarbonyl) and the like.

The heterocyclic group represented by R ₁₃ is selected from a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom,
It is a substituted or unsubstituted heterocyclic group having 1 to 16, preferably 1 to 10 carbon atoms. Representative heterocyclic groups include
Pyridyl group, furyl group, pyridinyl group, pyrazolyl group,
Examples include a pyrazinyl group and a pyrimidinyl group.

Z ₁₁ represents a hydrogen atom or a group or atom capable of leaving by a coupling reaction with an oxidized aromatic primary amine, and specific examples thereof have the same meaning as Z ₂₁ described in detail below.
A group represented by the following general formula (A) or (B) is preferred.

General formula (A) —O—R ₁ (wherein R ₁ represents an aryl group or a heterocyclic group) General formula (B) (In the formula, Z ₁ represents a nonmetallic atom group necessary for forming a 4- to 6-membered ring.) In the general formula (A), R ₁ is phenyl substituted with at least one electron-withdrawing group. Groups (eg, US Pat.
No. 933,501) are more preferable, and in the general formula (B), a non-metal atom group necessary for Z ₁ to form a 5- or 6-membered ring is more preferable. Preferred specific examples of the 5- or 6-membered ring are represented by the following formulas (VII) to (IX).

(Wherein, R ₇₁ , R ₇₂ , R ₈₁ , and R ₈₂ each represent a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amide group, an alkyl group,
Represents an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, a carbamoyl group (for example, an N-arylcarbamoyl group), an unsubstituted or substituted phenyl group or a heterocyclic group, The groups can be the same or different. ) (Where W ₉₁ is Together with a non-metallic atom required to form a 5- or 6-membered ring. More preferred specific examples of the general formula (IX) are the following formulas (X) to
(XII).

(Wherein, R ₁₀₁ and R ₁₀₂ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxyl group, and R ₁₀₃ , R ₁₀₄ and R ₁₀₅ represent a hydrogen atom, an alkyl group and an aryl group, respectively. , An aralkyl group or an acyl group, and W ₁₀₁ represents an oxygen or sulfur atom.) The coupler of the general formula (I) may form a dimer or a multimer.

 The general formula (II) will be described in detail.

In formula (II) R ₂₁ represents a hydrogen atom or a substituent, Z ₂₁ represents a removable group or atom in a reaction with an oxidation product of a hydrogen atom or an aromatic primary amine color developing agent, Z ₂₂ , Z ₂₃ and Z ₂₄ are -N = or represents -NH-, Z ₂₄ -Z ₂₃ bond and Z ₂₃ -Z ₂₂
One of the bonds is a double bond and the other is a single bond.
The case where Z ₂₃ -Z ₂₂ is a carbon-carbon double bond includes the case where it is a part of an aromatic ring.

In the general formula (II), R ₂₁ is preferably a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group,
Anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group , A sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.

To describe these substituents in more detail, R ₂₁ is a hydrogen atom, a halogen atom (eg, chlorine, bromine), an alkyl group (eg, methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3- (2 , 4-Di-t-amylphenoxy) propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsulfonyl-ethyl, cyclopentyl, benzyl), aryl group (eg, phenyl, 4-t-butylphenyl) , 2,4
-Di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2benzothiazolyl), a cyano group, an alkoxy group (eg, methoxy, ethoxy,
-Methoxyethoxy, 2-dodecyloxyethoxy, 2
-Methanesulfonylethoxy), an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy), a heterocyclic oxy group (eg, 2-benzimidazolyloxy), an acyloxy group (eg,
Acetoxy, hexadecanoyloxy), carbamoyloxy group (for example, N-phenylcarbamoyloxy,
N-ethylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy), a sulfonyloxy group (eg, dodecylsulfonyloxy), an acylamino group (eg, acetamido, benzimide, tetradecaneamide, α- (2,4-di-t- Amylphenoxy) butyramide, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide), anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, 2
-Chloro-5-dodecyloxycarbonylanilino, N
-Acetylanilino, 2-chloro-5- {α- (3-t
-Butyl-4-hydroxyphenoxy) dodecaneamide {anilino), a ureido group (eg, phenylureide, methylureide, N, N-dibutylureide), an imide group (eg, N-succinimide, 3-benzylhydantoinyl, 4) -(2-ethylhexanoylamino) phthalimide), a sulfamoylamino group (for example, N, N
-Dipropylsulfamoylamino), an alkylthio group (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (eg, Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
Tetradecanamidophenylthio), a heterocyclic thio group (for example, 2-benzothiazolylthio), an alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecylcarbonylamino), an aryloxycarbonylamino group (for example, phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), a sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t) -Butylbenzenesulfonamide), carbamoyl group (for example, N-
Ethylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-tert-amylphenoxy) propyl @ carbamoyl), an acyl group (eg, an acetyl group, (2,4-di-ter
t-amylphenoxy) acetyl, benzoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N,
N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl),
Sulfonyl group (for example, metal sulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl,
2-butoxy-5-tert-octylphenylsulfonyl), a sulfinyl group (eg, octanesulfinyl, dodecylsulfinyl, phenylsulfinyl),
Represents an alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, octadecylcarbonyl) or an aryloxycarbonyl group (eg, phenyloxycarbonyl, 3-pentadecyloxy-carbonyl).

Z ₂₁ represents a hydrogen atom or a group or atom capable of leaving in the reaction with an oxidized form of an aromatic primary amine color developing agent, and examples thereof include a halogen atom (for example,
Fluorine, chlorine, bromine) alkoxy groups (eg, dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, methanesulfonyloxy), aryloxy groups (eg,
4-methylphenoxy, 4-tert-butylphenoxy,
4-methoxyphenoxy, 4-methanesulfonylphenoxy, 4- (4-benzyloxyphenylsulfonyl)
Phenoxy), acyloxy groups (eg, acetoxy,
Tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), amide group (eg, dichloroacetylamino, methanesulfonylamino, triphonylphosphonamide), alkoxycarbonyloxy group (eg, Ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), aliphatic or aromatic thio group (for example, phenylthio, dodecylthio, benzylthio, 2-butoxy-5-tert-octylphenylthio) , 2,5-di-octyloxyphenylthio, 2- (2-ethoxyethoxy) -5-tert-octylphenylthio, tetrazolylthio), imide group (for example, succinimide, Toiniru, 2,4-dioxo oxazolidine-3-yl, 1-3-benzyl-4-ethoxy hydantoin yl), N- heterocyclic ring (e.g., 1
-Pyrazolyl, 1-benzotriazolyl, 5-chloro-
1,2,4-triazol-1-yl) and the like.

R ₂₁ or Z ₂₁ of the general formula (II) may form a dimer or a multimer.

 The general formula (III) will be described in detail.

In the general formula (III), R ₃₁ is an alkyl group having 1 to 32 carbon atoms, for example, a methyl group, a butyl group, a tridecyl group,
Examples of a cyclohexyl group and an allyl group include an aryl group such as a phenyl group and a naphthyl group. Examples of a heterocyclic group include a 2-pyridyl group and a 2-pyridyl group.
And a furyl group.

When R ₃₁ is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

R ₃₁ further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-t
ert-amylphenoxy, 3-tert-butyl-4-hydroxyphenyloxy, naphthyloxy), carboxy, alkyl or arylcarbonyl (eg, acetyl, tetradecanoyl, benzoyl), alkyl or aryloxycarbonyl (eg, Methoxycarbonyl, phenoxycarbonyl), acyloxy group (eg, acetyl, benzoyloxy), sulfamoyl group (eg, N-ethylsulfamoyl, N-octadecylsulfamoyl), carbamoyl group (eg,
N-ethylcarbamoyl, N-methyl-dodecylcarbamoyl), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), an acylamino group (eg, acetylamino, benzamide, ethoxycarbonylamino, phenylaminocarbonylamino),
Substituted with a substituent selected from an imide group (eg, succinimide, hydantoinyl), a sulfonyl group (eg, methanesulfonyl), a hydroxyl group, a cyano group, a nitro group, and a halogen atom (eg, chlorine, bromine, fluorine). Is also good.

R ₃₂ represents an acylamino group or an alkyl group.

Acylamino groups include unsubstituted acylamino groups (eg, acetamido, n-tetradecanamido, n-tridecanamido) and substituted acylamino groups. As a specific example of the substituent of the substituted acylamino group, a phenoxy group is preferable, but the phenoxy group may be substituted. Specific examples of the substituent of the substituted phenoxy group include an alkyl group (e.g., methyl, ethyl, n-hexadecyl, t-amyl), a halogen atom (e.g., a chlorine atom, a phenyl atom), an alkoxy group (e.g., methoxy, ethoxy), cyano Group, aryloxy group (eg, phenoxy), acylamino group (eg, methanesulfonamide, acetamide), imide group (eg, succinimide, n-octadecylsuccinimide), sulfamoyl group (eg, N-ethylsulfamoyl, n-octadecylsulfamoyl) ), An alkoxycarbonyl group (eg, ethoxycarbonyl), a sulfonyl group (eg, methylsulfonyl), a hydroxyl group, and the like.

The alkyl group is preferably an unsubstituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, n-propyl, t-
Butyl, t-octyl).

R ₃₃ represents a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom), an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy) or an amide group (eg, acetamido, methanesulfonamido). .

Attached at R ₃₂ and R _33, may form a 5- to 7-membered ring.

Z ₃₁ represents a hydrogen atom or a coupling-off group or atom, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and an alkoxy group (for example, dodecyloxy, methoxycarbamoylmethoxy, carboxy) Propyloxy, methylsulfonylethoxy), aryloxy group (eg, 4-chlorophenoxy, 4-methoxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg, methanesulfonyloxy) , Toluenesulfonyloxy), an amide group (eg, dichloroacetylamino, methanesulfonylamino, toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyl) Bonyloxy), an aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), an aliphatic or aromatic thio group (eg, phenylthio, tetrazolylthio), an imide group (eg, succinimide, hydantoinyl), an N-heterocyclic ring (eg, 1- Pyrazolyl, 1-benztriazolyl) and the like.

R ₃₁ or R ₃₂ of the general formula (III) may form a dimer or a multimer thereof.

More preferred yellow couplers of the general formula (I) are those wherein, in the general formula (I), R ₁₁ is a t-butyl group and R ₁₂ is a chlorine atom or an alkoxy group (for example, methoxy, hexadecyloxy); Z ₁₁ is the same as the general formula (I
X).

More preferred magenta couplers of the general formula (II) are the following general formula (IV), and more preferred cyan couplers of the general formula (III) are the following general formulas (V) or (VI)
Is represented by

General formula (IV) (Wherein, Z ₄₁ represents a hydrogen atom, a halogen atom, an aryloxy group or an arylthio group, R ₄₁ represents an alkyl group, an alkoxy group, or an aryloxy group;
₄₁ represents an alkylene group, arylene group or aralkylene group, X ₄₂ is -NHSO ₂ - group or And R ₄₂ represents an aryl group or an alkyl group. The alkyl group represented by R ₄₁ includes an unsubstituted alkyl group (eg, methyl, ethyl, t-butyl) and a substituted alkyl group. Examples of the substituent of the substituted alkyl group include an alkoxy group (for example, methoxy and ethoxy) and an aryl group (for example, phenyl, p-chlorophenyl, and m-tridecanamidophenyl). The alkoxy group represented by R ₄₁ is an unsubstituted alkoxy group (eg, methoxy, ethoxy)
And substituted alkoxy groups. Examples of the substituent of the substituted alkoxy group include the substituents described above for the alkyl group.

The aryl group of the aryloxy group represented by R ₄₁ includes an unsubstituted aryloxy group (for example, phenoxy) and a substituted aryloxy group. Specific examples of the substituent include an alkyl group (for example, methyl), an alkoxy group (for example, methoxy), a hydroxyl group, a halogen atom (for example, chlorine atom), and an amide group (for example, acetamido, methanesulfonamido). As the aryloxy group, a phenoxy group in which an alkoxy group is substituted at the ortho position is particularly preferable.

R ₄₁ is particularly preferably an alkyl group having 4 or less carbon atoms such as a methyl group, an ethyl group, an i-propyl group and a t-butyl group.

As X ₄₁ , an alkylene group (for example, methylene, ethylene, 1-methylethylene, 2-methylethylene, 2-methylpropylene, 1,2-dimethylethylene, 2,2-dimethylpropylene), an arylene group (for example, phenylene, 2-
Examples thereof include chlorophenylene, 2-t-butylphenylene) and aralkylene groups (for example, phenylene), and among them, a branched alkylene group is preferable.

The aryl group represented by R ₄₂ includes a phenyl group and a substituted phenyl group. Examples of the substituent include a substitutable group such as an alkyl group, an alkoxy group, a halogen atom, a sulfonamide group, a sulfamoyl group, an acylamide group, an alkoxycarbonyl group, a hydroxyl group, and a cyano group.

The alkyl group represented by R ₄₂ is an alkyl group having 1 to 36 carbon atoms (eg, methyl, ethyl, propyl, butyl,
Octyl, decyl, and pentadecyl), and may be further substituted with a substituent. As the substituent, a substituted or unsubstituted phenoxy group (for example, 2,4-di-t-amylphenoxy, 2-chloro-4-t-amylphenoxy,
-T-amylphenoxy, 2,4-di-t-octylphenoxy).

General formula (V) (Wherein, R ₅₁ represents an alkyl group having 1 to 15 carbon atoms, R ₅₂
Is an unsubstituted alkyl group having 1 to 32 carbon atoms or 7 to 32 carbon atoms
Represents an aryloxy-substituted alkyl group. The alkyl group having 1 to 15 carbon atoms represented by R ₅₁ may be any of a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, a t-butyl group, and an n-alkyl group.
Decyl group and the like.

The unsubstituted alkyl group having 1 to 32 carbon atoms represented by R ₅₂ may be any of a linear or branched alkyl group, and specific examples thereof include a pentadecyl group, an n-dodecyl group, an n-tetradecyl group, an n-decyl group, and an n- Tridecyl group, 2-ethylhexyl group, i-stearyl group, 1-ethyl, 1,3,6,8,8-
And a pentamethylnonyl group. The aryl group of the aryloxy-substituted alkyl group includes a phenyl group and a substituted phenyl group, and specific examples of the substituent include a halogen atom (eg, a chlorine atom), an alkyl group (eg, t-amyl,
t-octyl, methyl, ethyl), an amide group (eg, acetamido, methanesulfonamide), a cyano group, a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy).

General formula (VI) (In the formula, R ₆₁ represents an aryl group (for example, phenyl), and the aryl group may be substituted. Specific examples of the substituent include the substitution of the substituted phenyl group represented by R ₄₂ in the general formula (IV). Groups.

R ₆₂ has the same meaning as R _{52 in} formula (V).

R ₆₃ is hydrogen, alkyl or ortho Represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring together with the carbon atom of The non-metallic atom group represented by R ₆₃ includes an alkylene group, an amide group and the like. R ₆₃ R ₆₂ is absent when both form a 5- or 6-membered ring.

The alkylene group may be linear or branched, or may be an alkylene group containing a cyclic alkyl group.

Next, specific examples of the compounds of the general formulas (I) to (III) will be given, but the present invention is not limited thereto.

Compound of general formula (I) Compound of general formula (II) Compound of general formula (III) The couplers represented by the above general formulas (I), (II) and (III) may be used in the silver halide emulsion layer constituting the photosensitive layer in an amount of usually 0.1 to 1.0 mol per mol of the silver halide, preferably 0.1 to 1.0 mol. It is contained in the range of 0.1 to 0.5 mol.
The molar ratio between the couplers represented by formulas (I), (II) or (III) is usually about 1: 0.2 to 1.5:
Although it is often in the range of 0.5 to 1.5, it is possible to design a light-sensitive material outside this range.

The coupler represented by formula (I) used in the present invention can be easily synthesized by referring to U.S. Pat. No. 4,617,256, Japanese Patent Publication No. 62-61251, British Patent No. 909,319, and the like.

The couplers represented by formula (II) used in the present invention are described in JP-A-59-162548, JP-A-59-171956 and JP-A-60-33552.
Nos. 60-43659, U.S. Pat.Nos. 3,061,432 and 3,369,
The compounds can be synthesized by referring to Nos. 897 and 3,725,067.

The couplers represented by formula (III) used in the present invention are described in JP-A-56-80045, JP-A-59-31935, and JP-A-59-121332.
Nos. 59-124341 and 60-205446 can be easily synthesized.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having sensitivity in each wavelength range and a dye having a complementary color relationship with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By including a so-called color coupler, color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [single or multiple layers] and a so-called stacked structure particle having a different halogen composition, or
Particles having a structure having a different halogen composition in a non-layered manner inside or on the surface of the particle (in the case of being on the surface of the particle, a structure in which different composition portions are bonded on the edge, corner or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
It is more preferably at least 95 mol%.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described by P. Glafkides.
mie et Phisigue Photographique (published by Paul Montel,
1967), Photographic Emulsion Chem by GFDuffin
istry (Focal Press, 1966), VLZelikman et
al Making and Coating Photographic Emuldion
(Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. The spectral sensitizing dye used at this time is, for example, Heterocyclic com by FM Harmer.
pounds-Cyanine dyes and related compounds (John
Wiley & Sons [New York, London], 1964). Specific examples of the compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-215275.
What is described in the upper right column of page 22 to page 38 of the specification of Unexamined-Japanese-Patent No. 2000-216, is preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (A) General formula (B) W ₁ -COO-W ₂ General formula (C) General formula (D) Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW ₁
Wherein n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ form a condensed ring May be used).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of organic brown inhibitors are described in the following patent specifications.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, etc., hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. 5
No. 2-6623, etc., gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
No. 3,457,079, No. 4,332,886, JP-B-56-21144, etc., hindered amines are U.S. Pat.Nos. 3,336,135, 4,268,593, British Patents 1,326,889, 1,354,31.
No. 3, No. 1,410,846, JP-B-51-1420, JP-A-58-
Metal complexes are described in 114036, 59-53846, 59-78344, and the like, and U.S. Pat. Nos. 4,050,938 and 4,241,155 and British Patent 2,027,731 (A), respectively. These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec with p-anisidine. Is a compound that reacts with The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R _1- (A) _n -X General formula (FII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes addition of an aromatic amine-based developing agent to the compound of the general formula (FII). Represents a group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by the general formulas (FI) and (FII) are described in specifications such as JP-A-63-158545, JP-A-62-283338, EP-A-298321, and 277589. Are preferred.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilic _um CH ₃ I value (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
No. 229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

The color developer used in the development of the photosensitive material of the present invention is
Preferably, it is an aqueous alkaline solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

The color developing solution includes a pH buffer such as an alkali metal carbonate or phosphate, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or an antifoggant. It is common to include. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N, N ',
N'-tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal processing is performed, color development is usually performed after black-and-white development and reversal processing are performed. In this black and white developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. .

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 ml
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, the aperture ratio = the contact area between the treatment liquid and the air (cm ² ) / the volume of the treatment liquid (cm ³ ). The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05.

As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in Japanese Patent Application No. 62-241342, Examples of the method include a slit developing method described in JP-A-63-216050.

The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization.

Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further reduced by using a high temperature, a high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III) is used. A typical bleach is iron (II
Organic complex salts of I), for example, aminopolycarboxylic acids or citric acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid; Complex salts such as tartaric acid and malic acid can be used. Of these, aminopolycarboxylate iron (III) complex salts such as ethylenediaminetetraacetate iron (III) complex salt are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually
4.0 to 8.0, but lower for faster processing
It can be treated at pH.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
No. 5630, Research Disclosure No. 17,129 (1
A compound having a mercapto group or a disulfide bond described in, for example, Japanese Patent Application Laid-Open No. 50-140129; a thiourea derivative described in US Pat. No. 3,706,561; An iodide salt according to
Polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B No. 45-8836; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. Preservatives for the bleach-fix solution include sulfites and bisulfites, p
-Sulfinic acids such as toluenesulfinic acid or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
elevision Engineers Vol. 64, pp. 248-253 (5 May 1955)
Month) can be obtained.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, a method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry" ( 1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) A bactericide can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base-type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and metals described in U.S. Pat.No.3,719,492 Complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-11.
No. 5438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Example 1 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 15.3 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 4.4 g, (Cpd-2) 2.3 g and (Cpd-7) 1.8 g
27.2 cc of ethyl acetate and a solvent (Solv-3) and (Solv-
6) Each 4.1 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion (silver bromide 80.0 mol%, cubic; one with an average grain size of 0.85μ, variation coefficient 0.08, and one with silver bromide 80.0%, cubic, average grain size 0.62μ, variation coefficient 0.07) Were mixed at a ratio of 1: 3 (Ag mole ratio) to sulfur sensitized, and a blue-sensitive sensitizing dye shown below was added in an amount of 5.0 × 10 ^-4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(5.0 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ^-4 mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ⁻⁶ mol, 3.0 × 10 ⁻⁵ mol, 1.0 × 10 ⁻⁵ mol, and 2-methyl-5-t-octylhydroquinone in an amount of 8 × 10 ⁻³ mol, 2 × 10 −5 mol per mol of silver halide. ^-2 mol, 2 × 10 ^-2 mol were added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10
^-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

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

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion described above (AgBr: 80 mol% 0.21 gelatin 1.83 yellow coupler (ExY) 0.66 color image stabilizer (Cpd-1) 0.19〃 (Cpd-2) 0.10〃 (Cpd-7) 0.08 solvent (Solv-3) 0.14〃 (Solv-6) 0.14 second Layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 〃 (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, cube , An average particle size of 0.47μ and a coefficient of variation of 0.12, and an AgBr 90 mol%, cubic, average particle size of 0.36μ and a coefficient of variation of 0.09:
0.16 Gelatin 1.79 Magenta coupler (ExM) 0.22 Color image stabilizer (Cpd-3) 0.20〃 (Cpd-8) 0.03〃 (Cpd-4) 0.01〃 (Cpd-9) 0.04 Solvent (Solv-2) 0.65 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) The silver chlorobromide emulsion (AgBr 70 mol%, cubic, average grain size 0.49 μ, coefficient of variation 0.08, and AgBr 70 mol%, cubic, average grain size 0.34 μ, coefficient of variation 0.10:
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.30 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol ( Denaturation 17%) 0.17 Liquid paraffin 0.03 (Solv-3) solvent _{O = PO-C 9 H 19} (iso)) 3 The yellow coupler (ExY) represents the above exemplified coupler (I-1), the magenta coupler (ExM) represents the above exemplified coupler (II-3), and the cyan coupler (ExC) represents the above exemplified coupler (III-1). .

 The sample thus obtained was designated as 100.

Next, as shown in Table 1, samples 101 to 121 were prepared in the same manner except that the yellow coupler of the first layer, the magenta coupler of the third layer, and the cyan coupler of the fifth layer were changed.

The following couplers were used as comparative couplers.

The above photosensitive material was exposed through an optical wedge and processed in the following steps.

Processing temperature Time Color development 38 ° C 1 minute 40 seconds Bleaching and fixing 35 ° C 1 minute 00 seconds Rinse 33-35 ° C 20 seconds Rinse 33-35 ° C 20 seconds Rinse 33-35 ° C 20 seconds Drying 70-80 ° C 50 seconds (A three-tank countercurrent system was used for rinsing.) The composition of each processing solution was as follows. Color developer tank liquid water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Benzyl alcohol 16 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 0.5 g Potassium carbonate 30 g N- Ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.5 g Hydroxylamine sulfate 2.0 g Fluorescent whitening agent (WHITEX4 1.5 g, Sumitomo Chemical ) 1000 ml pH with water (25 ° C) 10.20 Bleaching and fixing solution tank solution Water 400 ml ammonium thiosulfate (70%) 80ml Sodium sulfite 24g Iron (III) ethylenediaminetetraacetate Ammonium 30g Disodium ethylenediaminetetraacetate 5g Add water 1000ml pH (25 ℃) 6.50 Rinse solution Ion exchange water (calcium and magnesium each 3ppm or less) The fog, gamma, and maximum density (Dmax) of each color were measured for each sample having a color dye image formed by the method described in Table 2. The results are shown in Table 2.

As is clear from Table 2, the samples of the present invention (100 to 11
2) has a higher color density without increasing fog, and has substantially the same gamma of yellow, magenta, and cyan as compared to the samples (113 to 121) using the comparative coupler, and has an excellent color balance.

Example 2 A multilayer color printing paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution 15.3 g of yellow coupler (ExY-2), 4.4 g of color image stabilizer (Cpd-1) and 0.7 g of color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and solvent (Solv-3) ) 8.2 g was added and dissolved, and this solution was emulsified and dispersed in 18.5 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (cubic average grain size 0.88μ
3: 7 mixture of the above and 0.70μ (silver molar ratio). The variation coefficient of the grain size distribution is 0.08 and 0.10, and each emulsion contains 0.2 mol% of silver bromide localized on the grain surface).
2.0 × 10 ⁻⁴ mol was added to each of the emulsions, and for small-sized emulsions, 2.5 × 10 ⁻⁴ mol was added and then subjected to sulfur sensitization. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dyes in each layer.

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

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

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

Support Polyethylene laminated paper [The polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY -2) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cube, average size 0.55μ,
1: 3 mixture with 0.39μ (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, and AgBr 0.8 for each emulsion.
0.12 gelatin 1.24 Magenta coupler (ExM-2) 0.14 stable color image (Cpd-3) 0.15 stable color image (Cpd-4) 0.02 color image stabilizer (Cpd- 2) 0.03 Solvent (Solv-2) 0.40 4th layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 5th layer (red Sensitive layer) Silver chlorobromide emulsion (cube, average size 0.58μ,
1: 4 mixture with 0.45μ (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, AgBr 0.6 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC-2) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-8) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.
17 Liquid paraffin 0.
03 (Solv-3) solvent _{O = PO-C 9 H 19} (iso)) 3 The yellow coupler (ExY-2) is the coupler (I)
-2), the magenta coupler (ExM-2) is the coupler (II
-3), the cyan coupler (ExC-2) is the coupler (III-
Each of 3) and (III-25) represents a 1: 1 mixture in molar ratio.

 The sample thus obtained was designated as 200.

Next, as shown in Table 3, samples 201 to 220 were prepared in the same manner except that the yellow coupler of the first layer, the magenta coupler of the third layer, and the cyan coupler of the fifth layer were changed.

The yellow coupler for comparison used was the one described in Example-1.

After the photosensitive material was imagewise exposed, continuous processing (running test) was performed using a paper processor until the replenishment of the tank volume for color development was doubled in the following processing steps.

Processing process temperature Time replenishment amount Tank capacity Color development 35 ° C 45 seconds 161ml 17l Bleaching and fixing 30-36 ° C 45 seconds 218ml 17l Rinse 30-37 ° C 30 seconds −10l Rinse 30-37 ° C 30 seconds −10l Rinse 30-37 ° C 30 sec 360 m 10l drying 70 to 80 ° C. 60 seconds photosensitive material 1m per ² (and the third tank countercurrent system to rinse →.) the composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (700g / l) 100ml Sodium sulfite 17g Iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium each 3ppm or less) For each sample having a color dye image formed by the above method, fog of each color, Gamma and maximum density (Dmax) were measured under the same conditions as in Example 1. The results are shown in Table 4.

As is clear from Table 4, the samples of the present invention (200 to 21)
2) was superior to the sample (213 to 220) using the comparative coupler in terms of color balance of the image, and was found to exhibit performance suitable for rapid processing.

(Effect of the Invention) According to the present invention, it is possible to obtain a multilayer silver halide color photographic light-sensitive material having good color developability and excellent yellow, magenta and cyan color balance.

Claims (1)

(57) [Claims] 1. A color photographic light-sensitive material having at least three kinds of light-sensitive silver halide emulsion layers having different color sensitivity on a support, wherein the first light-sensitive layer comprises a coupler represented by the following formula (I): The second photosensitive layer contains at least one kind of coupler represented by the following general formula (II), and the third photosensitive layer contains at least one kind of coupler represented by the following general formula (III). A silver halide color photographic light-sensitive material, characterized in that it contains at least one kind. General formula (I) (Wherein, R ₁₁ represents an alkyl group or an aryl group;
₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group, R ₁₃ represents an alkyl group, an aryl group or a heterocyclic group, and J ₁₁ represents -SO ₂ -or Represents a group represented by, J ₁₂ is -SO _2- , Or -CO ₂ - represents a group represented by, Z ₁₁ represents a group or atom capable of splitting off upon reaction with an oxidation product of hydrogen atoms or an aromatic primary amine developing agent. However, the following compounds are excluded. General formula (II) (Wherein, R ₂₁ represents a hydrogen atom or a substitutable group;
₂₁ represents a hydrogen atom or a group or atom which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent. However, R ₂₁ and Z ₂₁ do not simultaneously represent a hydrogen atom. Z ₂₂ , Z ₂₃ and Z ₂₄ are each -N = or represents -NH-, Z ₂₄ -Z ₂₃ bond and Z ₂₃ -Z ₂₂
One of the bonds is a double bond and the other is a single bond. The case where Z ₂₃ -Z ₂₂ is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. ) General formula (III) (Wherein, R ₃₁ represents an alkyl group, an aryl group, an amino group or a heterocyclic group, R ₃₂ represents an acylamino group or an alkyl group, and R ₃₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amide group. And R ₃₂ and R
₃₃ may combine to form a 5- to 7-membered ring. Z ₃₁ represents a hydrogen atom or a group or atom which can be eliminated in the reaction with an oxidized form of an aromatic primary amine color developing agent. )