JPH0534879A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material superior in storage stability, sharpness, graininess, and color reproduction performance. CONSTITUTION:The silver halide color photographic sensitive material contains a coupler represented by formula I in which R1 is a group combined through at least one O or N or S atom with another group, halogen, acyl, cyano, ora nitromethylated methyl: R2 is an aliphatic or aromatic group; R3 is H, or same as R2: each of Z1 and Z2 is, independently, =N- or =C(R4)-; R4 is H, halogen, an aliphatic, aromatic, or heterocyclic group, cyano, carboxy, hydroxy, alkoxy, aryloxy, heterocyclic-oxy, or the like; one of R1-R4 may be a divalent group and form the dimer of this coupler; and X is H or a group releasable by the coupling.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it contains a halogenated pyrazoloazole magenta coupler in which the hue and light fastness of a dye formed by development processing are improved. The present invention relates to a silver color photographic light-sensitive material.

[0002]

2. Description of the Related Art Pyrazoloazole-based magenta couplers, which have been actively researched in recent years, include US Pat.
1H-pyrazolo [1,5- b ] -1,2,4-described in Japanese Patent Publication No. 540,654 and Japanese Patent Publication No. 2-44051.
Triazole skeleton, US Pat. No. 3,725,067,
1H-pyrazolo [5,1- c ] -1, described in Japanese Patent Publication Nos. 47-27444 and 48-30895.
2,4-triazole skeleton, JP-A-59-162548
No., European Published Patent No. 119741 and WO86 / 02
1H-imidazo [1,2-
b ] pyrazole skeleton, 1H-pyrazolo [1,5- d ] tetrazole skeleton described in JP-A-60-33552 and the like are known. Further, pyrazoloazole magenta couplers in which the 6-position is substituted with an oxygen atom, which improves photographic performance such as sensitivity, gradation and color density of a light-sensitive material using these couplers, are disclosed in JP-A-62-209457 and JP-A-6-209457. No. 2-161430. However, the pyrazoloazole magenta couplers in which the 6-position is substituted with an oxygen atom described in these specifications do not have sufficient fastness to light of the dye formed by the development processing, and the dye in the light-sensitive material after the processing is dyed. However, there is a problem in that the absorption spectrum tends to broaden and the absorption spectrum tends to be broad.

Further, DIR couplers having a pyrazoloazole skeleton are disclosed in JP-A-61-28947 and the like, but those DIR couplers are not those having sufficient performance in terms of the layering effect and the improvement of sharpness. There wasn't. Also,
The DIR coupler described in JP-A-3-142447 achieves both thermal stability improvement and multilayer effect and sharpness improvement to some extent, but further improvement in multilayer effect and sharpness is desired. It was rare. Further, although the light-sensitive material containing the coupler described in the specification has high thermal stability of the coupler, if the light-sensitive material before development is stored under conditions of high temperature and high humidity, sensitivity tends to decrease. As a result, it was necessary to improve this point.

[0004]

The object of the present invention is to provide a first object.
In addition, by developing a pyrazoloazole magenta coupler in which the light fastness of the dye after development is improved, and the dye exhibits sharp absorption characteristics in the light-sensitive material, a halogen image excellent in color image light fastness and color reproducibility is developed. A silver halide color photographic light-sensitive material is provided. Further, the second object of the present invention is to
Developed a magenta-colored DIR coupler that has a large effect of improving the layering effect and sharpness, and has solved the problems of the storage stability of the light-sensitive material before the development processing and the light fastness and absorption characteristics of the dye formed by the development processing. Accordingly, the object is to provide a silver halide color photographic light-sensitive material having excellent storage stability, sharpness, graininess, color image fastness and color reproducibility.

[0005]

The object of the present invention has been achieved by a silver halide color photographic light-sensitive material containing a coupler represented by the general formula (I) represented by the following chemical formula 2.

[0006]

[Chemical 2] (In the formula, R ₁ represents a methyl group to which a substituent linked by at least one oxygen atom, nitrogen atom or sulfur atom, a halogen atom, an acyl group, a cyano group or a nitromethyl group is bonded, and R ₂ is an aliphatic group or Represents an aromatic group, R
₃ represents a hydrogen atom, an aliphatic group or an aromatic group. Z ₁
And Z ₂ each represent a nitrogen atom or = C (R ₄ )-, and when Z ₁ and Z ₂ are both = C (R ₄ )-, 2
The two R _{4 s} may be the same or different. R ₄ is a hydrogen atom, halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, sulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, amide group, alkoxycarbonyl It represents an amino group, a ureido group, a sulfonamide group, a sulfamoylamino group, an azo group, a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfinyl group, a sulfonyl group, a sulfamoyl group, a sulfo group and a phosphinyl group. R _{1 to} R ₄ may form a bis form with a divalent group. X represents a hydrogen atom or a coupling-off group. )

The inventors of the present invention have made extensive studies by paying attention to the substituent and coupling-off group of the carbon atom adjacent to the coupling active position of the pyrazoloazole magenta coupler, and as a result, have studied the electronic effect of the substituent. By controlling the and the steric effect, a magenta color forming coupler and a DIR coupler which achieve the object of the present invention have been reached.

The compound represented by formula (I) of the present invention will be described in detail below. R ₁ has ₁ to 32 carbon atoms
A group of, at least one oxygen atom, a substituent linked by a nitrogen atom or a sulfur atom, a halogen atom, an acyl group,
It represents a methyl group to which a cyano group or a nitromethyl group is bonded, and examples thereof include phenoxymethyl, 4-chlorophenoxymethyl, 1-phenyl-1-hydroxymethyl, hydroxymethyl, methoxymethyl, ethoxymethyl, butoxymethyl, acetoxymethyl, methanesulfone. Amidomethyl, p-toluenesulfonamidomethyl, acetamidomethyl, N, N-dimethylaminomethyl, N-phenylaminomethyl, N-pyrazolylmethyl, N-morpholinomethyl, nitromethyl, methylthiomethyl, butylthiomethyl, phenylthiomethyl, benzene Sulfonylmethyl, methanesulfonylmethyl, trifluoromethyl,
Represents trichloromethyl, difluoromethyl, dichloromethyl, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, acetonyl, carboxymethyl, 2-nitroethyl, and those which can have a substituent further have a substituent. However, preferable substituents are the same as the substituents represented by R ₄ .

The aliphatic group represented by R ₂ has 1 to 3 carbon atoms.
2 straight-chain, branched or cyclic alkyl, alkenyl or alkynyl groups represent, for example, methyl, ethyl, propyl, isopropyl, 1-butyl, t-butyl, cyclopropyl, cyclohexyl, vinyl, acetylenyl. The aromatic group represented by R ₂ is an aromatic group having 6 to 32 carbon atoms and represents, for example, phenyl, 1-naphthyl or 2-naphthyl. The aliphatic group and aromatic group represented by R ₂ may further have a substituent, and preferable substituents are the same as those of R ₄ .

The aliphatic group or aromatic group represented by R ₃ has the same meaning as the aliphatic group or aromatic group represented by R ₂ described above.

R ₄ is a hydrogen atom or a halogen atom (for example,
A fluorine atom, a chlorine atom), an aliphatic group (a linear, branched or cyclic alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group or an alkynyl group, for example, methyl,
Ethyl, isopropyl, 1-butyl, t-butyl, 1-
Octyl, tridecyl, 2-methanesulfonylethyl,
3- (3-pentadecylphenoxy) propyl, 3-
{4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy ) Propyl), an aryl group (an aryl group having 6 to 32 carbon atoms, for example, phenyl, p-tolyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-nitrophenyl, 4- Ethoxyphenyl, 1-naphthyl), a heterocyclic group (a saturated or unsaturated heterocyclic group having 1 to 32 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl 1 −
Piperidinyl), cyano group, carboxyl group, hydroxyl group, alkoxy group (alkoxy group having 1 to 32 carbon atoms, for example, methoxy, ethoxy, 1-butoxy), aryloxy group (aryloxy group having 6 to 32 carbon atoms) , For example, phenoxy, 2-methoxyphenoxy, 4
-Nitrophenoxy, 3-butanesulfonamidophenoxy, 2,5-di-t-amylphenoxy, 2-naphthoxy), a heterocyclic oxy group (a heterocyclic oxy group having 1 to 32 carbon atoms, for example, 2-furyloxy , 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (acyloxy group having 1 to 32 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy, etc.), alkoxycarbonyloxy group (With an alkoxycarbonyloxy group having 1 to 32 carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, 2-ethyl-1-
Hexyloxycarbonyloxy), an aryloxycarbonyloxy group (an aryloxycarbonyloxy group having 6 to 32 carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group (a carbamoyloxy group having 1 to 32 carbon atoms, for example, N , N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (a sulfamoyloxy group having a carbon number of 32 or less, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyl) Oxy), a sulfonyloxy group (a sulfonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, benzenesulfonyloxy), an acyl group (an acyl group having 1 to 32 carbon atoms, for example, acetyl, pivaloyl, benzoyl) , Alkoxycarbonyl group An alkoxycarbonyl group having 2 to 32 carbon atoms, for example, ethoxycarbonyl, isobutyloxycarbonyl), an aryloxycarbonyl group (an aryloxycarbonyl group having 7 to 32 carbon atoms, for example, phenoxycarbonyl), a carbamoyl group (having 1 carbon atom). To 32 carbamoyl groups, for example, N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), amino groups (amino groups having 32 or less carbon atoms, such as amino and N-methyl). Amino, N, N-dioctylamino), anilino group (an anilino group having 6 to 32 carbon atoms, for example, N-methylanilino, 2-chloro-5-tetradecanamidoanilino, 2
-Chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), heterocyclic amino (heterocyclic amino group having 1 to 32 carbon atoms, for example, 4-pyridylamino), amide Group (C1-C32
An amide group of, for example, acetamide, benzamide,
Tetradecanoamide, 2- (2,4-di-t-amylphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} dodecaneamide),
Alkoxycarbonylamino group (alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, t-butoxycarbonylamino, ethoxycarbonylamino), ureido group (ureido group having 1 to 32 carbon atoms, for example, N, N
-Dimethylureido, N-phenylureido), a sulfonamide group (a sulfonamide group having 1 to 32 carbon atoms, such as methanesulfonamide, butanesulfonamide,
p-toluenesulfonamide, 2-octyloxy-5
-T-octylbenzenesulfonamide), a sulfamoylamino group (a sulfamoylamino group having a carbon number of 32 or less, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino) ),
Azo groups (Azo groups having 32 or less carbon atoms, such as phenylazo and 4-methoxyphenylazo), nitro groups, alkylthio groups (alkylthio groups having 1 to 32 carbon atoms, such as ethylthio, octylthio, tetradecylthio, 3
-Phenoxypropylthio), an arylthio group (an arylthio group having 6 to 32 carbon atoms, for example, phenylthio,
4-dodecylphenylthio, 2-butoxy-4-t-octylphenylthio, 4-tetradecaneamidophenylthio), a heterocyclic thio group (a heterocyclic thio group having 1 to 32 carbon atoms, for example, 1-phenyltetrazoli Ru-5-thio), a sulfinyl group (a sulfinyl group having 1 to 32 carbon atoms, for example, benzenesulfinyl, 3,5-di-
(Dodecyloxycarbonyl) benzenesulfinyl), a sulfonyl group (a sulfonyl group having 1 to 32 carbon atoms, for example, methanesulfonyl, octanesulfonyl,
p-toluenesulfonyl), a sulfamoyl group (a sulfamoyl group having 32 or less carbon atoms, for example, N, N-dimethylsulfamoyl, N, N-dibutylsulfamoyl), a sulfo group, and a phosphinyl group. Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Next, preferred ranges of these substituents will be described. R ₁ is preferably an alkoxymethyl group or an aryloxymethyl group represented by the following general formula (L-1), and when R ₁ is an aryloxymethyl group, the light fastness of the dye is particularly excellent. General formula (L-1) R < ₁₁ > -O-CH < ₂ > -In formula, R < ₁₁ > has a C1-C30 alkyl group (for example, methyl, ethyl, propyl, isopropyl, butyl, octyl, decyl), or C6-C6. It represents 30 aromatic groups (eg phenyl, p-chlorophenyl, p-methoxyphenyl, p-tolyl, p-acetamidophenyl, p-cyanophenyl).

R ₂ is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, and more preferably an alkyl group.

R ₃ is preferably a hydrogen atom, having 1 to 1 carbon atoms.
0 is an alkyl group or a phenyl group, more preferably a hydrogen atom.

R ₄ is preferably an alkyl group or an aromatic group, and an aromatic group is particularly preferable in that the layering effect and the sharpness improving effect are greater. Preferred alkyl groups as R ₄ are those represented by the following general formula (L-2).

General formula (L-2) -C (R ₄₁ ) (R ₄₂ ) -R ₄₃

In the formula, R ₄₃ has the same meaning as the preferred substituent of the group represented by R ₁ , and R ₄₁ and R ₄₂ each represent an alkyl group having 1 to 32 carbon atoms. The alkyl group represented by R ₄₁ or R ₄₂ is preferably an alkyl group having a carbon number of 32 or less (eg, methyl, ethyl,
Propyl, hexyl, nonyl, undecyl, tridecyl, hexadecyl), which may further have a substituent. R ₄₃ is preferably a hydrogen atom or an alkyl group, and preferred examples of the alkyl group are the same as those listed as the preferred examples of the alkyl group represented by R ₄₁ , which may further have a substituent. .. When the groups represented by R ₄₁ , R ₄₂ and R ₄₃ further have a substituent, preferred substituents are the same as those listed as the group represented by R ₄ .

A preferred aryl group for R ₄ is a phenyl group, which may have a substituent. When it further has a substituent, preferable substituents are the same as those mentioned as the group represented by R ₄ .

The coupling leaving group represented by X in the general formula (I) may be any conventionally known leaving group. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an acylamino group, an alkyl or aryl sulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, an aryl or It represents a heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic group, and an arylazo group, and these groups may further have a substituent. When it further has a substituent, preferable substituents are the same as those mentioned as the group represented by R ₄ . These leaving groups are non-photographic useful groups or photographic useful groups or their precursors (for example, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, oxidized developing agents). Scavenger, fluorescent dye, developing agent or electron transfer agent).

When X is a photographically useful group, those conventionally known are useful. For example, US Pat. No. 4,24
8,962, 4,409,323, 4,43
8,193, 4,421,845, 4,61
8,571, 4,652,516, 4,86
1,701, 4,782,012, 4,85
7,440, 4,847,185, 4,47
7,563, 4,438,193, 4,62
8,024, 4,618,571, 4,74
1,994, European Published Patent No. 193389A
No. 348139A or No. 272573A, or a leaving group (for example, a timing group) for releasing the photographically useful group is used.

When the group represented by X in the general formula (I) represents a development inhibitor residue, examples of the development inhibitor include, for example, US Pat. No. 4,477,563 and JP-A-60-2.
18644, 60-211750, 60-23
And those described in No. 3650 or No. 61-11743.

The preferred development inhibitor residue represented by X in the general formula (I) is represented by the following general formula (II).

General formula (II) * -Y _1- (Y ₂ -L-Y ₃ ) _a

(In the formula, the * mark represents the position of bonding to the pyrazolotriazole nucleus in the general formula (I), Y ₁ represents the basic skeleton of the development inhibitor, and Y ₂ represents ₂ having 8 or less carbon atoms.
Represents a valent linking group or a simple bond, and L is a compound represented by the general formula (II) when it flows out into a developer,
Represents a linking group containing a bond which is cleaved by a developer, and Y
₃ represents a group for exhibiting a development inhibitory action. a is 0
Represents an integer of 3 to 3. )

The group represented by Y ₁ is a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, an imidazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a benzoxazolylthio group. Typical examples are a tetrazolylseleno group, a benzotriazolyl group, a triazolyl group substituted with an alkylthio group, and a benzimidazolyl group.

The above development inhibitor, after being cleaved from the pyrazolotriazole nucleus of the general formula (I), diffuses in the photographic layer while exhibiting a development inhibiting action and partially flows out into the developing solution.
When a is not 0 in the general formula (II), the development inhibitor that has flowed out into the developing solution reacts with hydroxyl ions or hydroxylamine generally contained in the processing solution and is contained in L. The bond portion is rapidly decomposed (for example, ester bond is hydrolyzed), the group represented by Y ₃ is cleaved, and the compound becomes a highly water-soluble compound having a small development inhibitory property, so that the development inhibitory effect is substantially disappeared.

The divalent group represented by Y ₂ is preferably --O--, --S--, --NHCO--, --SO ₂ -,-.
CO- or -NHSO ₂ - 2 also aliphatic include group or aromatic containing heteroatoms such as represented in
Represents a valent linking group or a simple bond. When Y ₂ represents a divalent linking group, examples of Y ₂ include methylene, ethylene, propylene, —CH (CH ₃ ) —, and —SCH _{2.
-, - SCH (CH 3)} -, - CH 2 OCH 2 -, - S
CH ₂ CH ₂ - or -CH ₂ SCH ₂ - group.

The linking group represented by L includes a chemical bond which is cleaved in the developing solution. Such chemical bonds include the following. Each of these is cleaved by a nucleophilic reactive agent such as hydroxyl ion or hydroxylamine which is a component in the color developing solution.

Chemical bond contained in L Cleavage reaction of the above-mentioned bond (reaction with OH ⁻ ) —COO— —COOH + HO— —NHCOO— —NH ₂ + HO— —SO ₂ O— —SO ₃ H + HO _{- -CH 2 CH 2 SO 2 -} -OH + CH 2 = CHSO 2 - -OCO 2 - -OH + HO- -NHCOCO 2 - -NH 2 + HO-

In the case of a heterocycle or a benzene condensed ring which constitutes the development inhibitor, the linking group represented by L is linked to the benzene ring through Y ₂ and directly to Y ₃ .

Y ₃ is a saturated or unsaturated, linear, branched or cyclic aliphatic group having 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, hexyl, trifluoromethyl (eg, 3-methyl-1 -Butoxy) carbonylmethyl, 1-butoxycarbonylmethyl, 1-pentylaminocarbonylmethyl, allyl, propargyl, cyclohexyl), an aromatic group having 6 to 18 carbon atoms (for example, phenyl, naphthyl) or a hetero group having 1 to 12 carbon atoms. Cyclic group (for example, 2-pyridyl, 4-pyridyl, 2-furyl, 2-
Tetrahydrofuryl, 4-pyrazolyl), and more preferably Y ₃ is an aliphatic group having 1 to 10 carbon atoms or a phenyl group. The group represented by Y ₃ may further have a substituent, preferred substituents are the same as those enumerated as the substituents of the group represented by R ₁ , and more preferably a halogen atom and a carbon number of 1 An alkoxy group of -10,
An aryloxy group having 6 to 10 carbon atoms, a heterocyclic oxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms,
Alkoxycarbonyloxy group having 2 to 10 carbon atoms, aryloxycarbonyloxy group having 7 to 10 carbon atoms, carbamoyloxy group having 1 to 10 carbon atoms, sulfamoyloxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms Sulfonyloxy group, C1-10 acyl group, C2-10
Alkoxycarbonyl group, C7-10 aryloxycarbonyl group, C1-10 carbamoyl group, C1-10 amino group, C6-10 anilino group, C1-10 hetero. Ring amino group, carbon number 1
-10 amide group, C 2-10 alkoxycarbonylamino group, C 1-10 ureido group, C 1
-10 sulfonamide group, C 1-10 sulfamoylamino group, nitro group, C 1-10 alkylthio group, C 6-10 arylthio group, C 1
And a heterocyclic thio group having 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a sulfonyl group having 1 to 10 carbon atoms, and a sulfamoyl group having 1 to 10 carbon atoms.

Particularly preferred development inhibitors represented by X in the general formula (I) are those represented by the following general formula (DI-
1) and (DI-2).

[0033]

[Chemical 3]

[0034]

[Chemical 4] (In the formula, * represents a position to be bonded to the pyrazolotriazole nucleus in the general formula (I). Z ₃ represents a non-necessary group to form a hetero ring (monocyclic ring or condensed ring) together with a carbon atom and a nitrogen atom. It represents a metal atom group, Z ₄ is .Y ₂ and Y ₃ represents a non-metallic atomic group necessary for forming a heterocyclic ring (monocyclic or condensed) together with the nitrogen atom of Y ₂ and in formula (II) It has the same meaning as Y _3. )

Z ₃ is preferably 5 together with -C = N-.
Represents a non-metallic atomic group necessary for forming a heterocycle of 7 to 7 membered ring which may be substituted or condensed. Examples of such heterocycles include triazole, tetrazole, oxadiazole, thiadiazole, benzimidazole or benzothiazole. Of these, particularly preferred are 1,2,4-triazole, tetrazole, 1,3,4-oxadiazole,
It is 1,3,4-thiadiazole.

Z ₄ is preferably 5 to 5 together with the nitrogen atom.
It represents a non-metallic atomic group necessary for forming a 7-membered hetero ring which may be substituted or condensed. Examples of such heterocycles include imidazole, 1,2,
4-triazole, 1,2,3-triazole, benzotriazole, pyrazole, indazole, imidazolidine-2-thione, oxazolidine-2-thione, 1,
2,4-triazoline-3-thione or 1,3,4-thiadiazoline-2-thione may be mentioned. Particularly preferred among these are 1,2,3-triazole and benzotriazole.

[0037] When the formula hetero ring represented by (DI-1) and (DI-2) has a substituent at a substitutable position in addition to -Y ₂ -L-Y _3, preferred substituents for R ₃ It is the same as those mentioned as the group represented, more preferably a halogen atom, an alkoxy group having 1 to 10 carbon atoms,
C6-C10 aryl group, C1-C10 heterocyclic group, C1-C10 acyloxy group, C2-1
0 alkoxycarbonyloxy group, C7-10 aryloxycarbonyloxy group, C1-10 carbamoyloxy group, C1-10 sulfamoyloxy group, C1-10 sulfonyl Oxy group,
C1-10 acyl group, C2-10 alkoxycarbonyl group, C7-10 aryloxycarbonyl group, C1-10 carbamoyl group, C1
-10 amide group, C 2-10 alkoxycarbonylamino group, C 1-10 ureido group, C 1
-10 sulfonamide group, C 1-10 sulfamoylamino group, nitro group, C 1-10 alkylthio group, C 6-10 arylthio group, C 1
And a heterocyclic thio group having 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, a sulfonyl group having 1 to 10 carbon atoms, and a sulfamoyl group having 1 to 10 carbon atoms.

More preferred as the development inhibitor residue represented by X in the general formula (I) are those represented by the following general formula (D).
I-3) and (DI-4), and the one represented by the general formula (DI-4) is the most preferable in terms of the effect of layering and the effect of improving graininess.

[0039]

[Chemical 5]

[0040]

[Chemical 6] (In the formula, the * mark represents the position bonded to the pyrazolotriazole nucleus in the general formula (I). Z ₃ , Z ₄ , Y ₂ and Y ₃ are the same as those in the general formulas (DI-1) and (DI-2). Z
It has the same meaning as ₃ , Z ₄ , Y ₂ and Y ₃ . )

Specific examples of the development inhibitor residue represented by the general formula (II) of the present invention are shown below, but the present invention is not limited thereto.

[0042]

[Chemical 7]

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

When the group represented by X in the general formula (I) represents a group other than the development inhibitor residue, X preferably represents a substituted or unsubstituted azolyl group, more preferably a substituted or unsubstituted pyrazolyl group. Represents a group. X
Is a substituted or unsubstituted pyrazolyl group, the photographic material storability of the silver halide color photographic light-sensitive material was particularly excellent. Specific examples of the azolyl group preferable as X are shown below, but the present invention is not limited thereto.

[0047]

[Chemical 11]

[0048]

[Chemical formula 12]

The coupler represented by the general formula (I) includes
The couplers represented by the following general formulas (III), (IV), (V) and (VI) are included.
The couplers represented by (III) and (IV) are particularly preferable from the viewpoint of thermal stability, and the coupler represented by the general formula (III) is particularly preferable because of high coupling reactivity with an oxidized product of a developing agent.

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054] (the same meaning as in formula _{in, R 1, R 2, R} 3, R 1 R 4 and X in the general formula _{(I), R 2, R} 3, R 4 and X. In addition, the general formula Two Rs in (V)
_Two may combine to form an aromatic ring. )

The compound represented by the general formula (I) may form a dimer or higher multimer through a divalent or higher valent group in the substituent R ₁ , R ₂ , R ₃ or R ₄ . When the compound represented by the general formula (I) forms a multimer, a homopolymer or a copolymer of the addition-polymerizable ethylenically unsaturated compound (color-forming monomer) having the above compound residue is typical. In this case the multimer contains repeating units of the general formula (VII). One or more kinds of color-forming repeating units may be contained in the multimer, and the copolymer may be a copolymer containing one or more non-color-forming ethylene-like monomers.

[0056]

[Chemical 17] (In the formula, R ₃₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, E represents —CONH—, —CO ₂ — or a substituted or unsubstituted phenylene group, and G represents a substituted or unsubstituted group. Represents a substituted alkylene group, a phenylene group or an aralkylene group, and T is -CONH-, -NHC
_{ONH -, - NHCO 2 -,} - NHCO -, - OCON
H -, - NH -, - CO 2 -, - OCO -, - CO-,
_{-O -, - SO 2 -,} - NHSO 2 - or -SO ₂ NH
Represents-. f, g and t represent 0 or 1, but f,
Neither g nor t is 0. QQ represents a compound residue in which a hydrogen atom has been removed from the compound represented by the general formula (I).

As the multimer, a copolymer of a compound monomer giving the compound unit of the general formula (VII) and the following non-color forming ethylene-like monomer is preferable.

As the non-color forming ethylene-like monomer which does not couple with the oxidation product of the aromatic primary amine developing agent,
Acrylic acid, α-chloroacrylic acid, α-alacrylic acid (eg, methacrylic acid) Esters or amides derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide) , Diacetone acrylamide, methylene bis acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate,
n-butyl acrylate, t-butyl acrylate, i
so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate and β-hydroxymethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, eg vinyltoluene). , Divinylbenzene, vinylacetophenone and sulfostyrene) itaconic acid, citracone, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether) maleic acid ester, N
-Vinyl-2-pyrrolidone, N-vinylpyridine and the like.

Particularly preferred are acrylic acid ester, methacrylic acid ester and maleic acid ester. Two or more kinds of non-color-forming ethylenic monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers,
When synthesizing the polymer coupler containing the repeating unit represented by the general formula (VII), the non-color-forming ethylene-like monomer copolymerized with the ethylene-like monomer having a coupler residue of the present invention is a copolymer formed. The physical and / or chemical properties of the polymer, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its plasticity, thermal stability, etc., can be selected to be favorably affected. ..

A solution of the polymer compound used in the present invention (a lipophilic polymer compound obtained by polymerization of a vinyl-type monomer giving the compound unit represented by the general formula (VII)) in an organic solvent is used as an aqueous gelatin solution. It may be prepared by emulsifying and dispersing in the form of latex therein, or may be prepared by direct emulsion polymerization method.

Lipophilic polymer compound A method for emulsion-dispersing in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820. For emulsion polymerization, US Pat. The method described in 370,952 can be used.

The typical examples of the compounds represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0064]

[Chemical 18]

[0065]

[Chemical 19]

[0066]

[Chemical 20]

[0067]

[Chemical 21]

[0068]

[Chemical formula 22]

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

The method for synthesizing the compound represented by formula (I) of the present invention will be described below. Of the compounds represented by the general formula (I), 1H-pyrazolo [1,5- b ] -1,2,4 contained in the compounds represented by the general formula (III)
The triazole skeleton is described in U.S. Pat. No. 4,540,654
No. 2, Japanese Patent Publication No. 2-44051, JP-A-60-17298.
No. 2, No. 60-215687, No. 60-197688
No. 60-190779 and No. 62-209457.
No. 63-41851, No. 63-307453, and the like.

Of the compounds represented by the general formula (I),
The 1H-pyrazolo [5,1- c ] -1,2,4-triazole skeleton contained in the compound represented by the general formula (IV) has a skeleton of US Pat. No. 3,725,067 and JP-B-47-2744.
4, JP-A-48-30895, JP-A-61-18780.
No. 62-33177, JP-A-1-233285, and the like.

Among the compounds represented by the general formula (I),
The 1H-imidazo [1,2- b ] pyrazole skeleton contained in the compound represented by the general formula (V) is disclosed in JP-A-59-16.
2548, EP 119741 and WO8.
It can be synthesized by the method described in 6/02467.

Of the compounds represented by the general formula (I),
The 1H-pyrazolo [1,5- d ] tetrazole skeleton contained in the compound represented by the general formula (VI) is disclosed in JP-A-60-3.
It can be synthesized by the method described in the specification of No. 3552.

Introduction of a coupling-off group is described in JP-A 2-5.
It can be carried out as follows by the method described in the specification of No. 9584. That is, it is a method in which the coupling active position of pyrazoloazole is brominated with a reaction agent such as N-bromosuccinimide or bromine, and then a development inhibitor group is introduced.

[0083]

[Chemical 32] _{(Wherein, R 1, R 2, R} 3, Z 1, Z 2 and X have the same meanings as _{R 1, R 2, R 3} , Z 1, Z 2 and X in the general formula (I).)

The base used in the above reaction (2) is an inorganic base such as sodium hydride or lithium aluminum hydride, or potassium t-butoxide, sodium ethoxide, sodium methoxide, triethylamine,
N, N, N, N-tetramethylguanidine, 2,6-lutidine, 1,8-diazabicyclo [5,4,0] -7-
Organic bases such as undecene (DBU) are preferred. The solvent used in the reaction (2) is preferably an aprotic polar solvent, for example, 1,3-dimethylimidazolidine-2.
-One, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone (DMPU), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-dimethyl. Acetamide (DM
AC) and acetonitrile.

X is the general formula (DI-1) or (DI-
In the case of the group represented by 3) or the arylthio group or the heterocyclic group, the ring thio group can also be synthesized by the reaction represented by the following formula.

[0086]

[Chemical 33] (.Y representing where the same meaning as _{R 1, R 2, R 3} , Z 1, R 1 in the Z ₂ and X have the general formula _{(I), R 2, R} 3, Z 1, Z 2 and X Represents a halogen atom (eg, chlorine atom, bromine atom), imide group (eg, succinimide group, phthalimido group), sulfonyl group (eg, benzenesulfonyl group), etc.)

The preferred solvent used in this reaction is
Aprotic polar solvent such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), acetonitrile, tetrahydrofuran, 1,4-
Examples thereof include ether solvents such as dioxane and 1,2-dimethoxyethane, halogen solvents such as dichloromethane, chloroform and 1,2-dichloroethane, and ethyl acetate.

Specific synthetic examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of Exemplified Compound (11)) Synthesis was carried out by the reaction shown in Chemical Formula 40 below.

[0090]

[Chemical 34]

25.0 g (23.7 mmol) of intermediate (A) was dissolved in 150 ml of chloroform and cooled in a water bath while stirring. To this, 4.18 g (23.5 mmol) of N-bromosuccinimide was added and stirred for 25 minutes. The reaction mixture was washed twice with 100 ml of water, dried over anhydrous sodium sulfate, and concentrated to obtain intermediate (B). 1,3-dimethylimidazolidine-2-
2.96 g (74.1 mm) of sodium hydride (dispersed in mineral oil, content 60% by weight) in 80 ml of ON (DMI)
ol) was added and the mixture was cooled in an ice-water bath with stirring. To this, 21.6 g (74.1 mmol) of intermediate (C) was added little by little over 20 minutes. After removing the ice water bath and stirring for 10 minutes, 40 ml of DMI was added to the intermediate (B) synthesized above.
The solution dissolved in was added, and the mixture was stirred at 45 ° C. for 0.5 hours and further at 55 ° C. for 1.5 hours. After cooling, the reaction mixture was extracted with 400 ml of ethyl acetate and 500 ml of water. The organic layer was washed twice with 300 ml of saturated aqueous sodium hydrogen carbonate and once with 300 ml of dilute hydrochloric acid.
The extract was washed once with 300 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) to prepare Exemplified Compound (11) 1.
6.2 g (yield 50%) was obtained as a pale yellow-orange glassy solid. Mass spectrum (FAB, Negative) m / e = 130
0 ([M-H] ^- )

Synthesis Example 2 (Synthesis of Exemplified Compound (5)) Synthesis was carried out by the reaction shown in Chemical Formula 41 below.

[0093]

[Chemical 35]

18.0 g (17.2 mmol) of intermediate (D) was dissolved in 150 ml of chloroform and cooled with stirring in a water bath. N-bromosuccinimide 2.
90 g (16.3 mmol) was added and stirred for 15 minutes. The reaction mixture was washed twice with 100 ml of water, dried over anhydrous magnesium sulfate and concentrated to give intermediate (E). 1,3-Dimethylimidazolidin-2-one (DM
I) 2.06 g (51.6 mmol) of sodium hydride (dispersed in mineral oil, content 60% by weight) was added to 50 ml, and the mixture was cooled in an ice-water bath with stirring. Intermediate to this (C)
15.0 g (51.6 mmol) was added portionwise over 15 minutes. The ice-water bath was removed, the mixture was further stirred for 10 minutes, then the intermediate (E) synthesized above was added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling, 200 ml of ethyl acetate was added to the reaction mixture.
And 200 ml of water were added for extraction. The organic layer was washed twice with 200 ml of saturated aqueous sodium hydrogen carbonate, once with 200 ml of dilute hydrochloric acid, and further washed with 200 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) to give Exemplified compound (5) 12.0 (yield 52).
%) As a pale yellow-orange glassy solid. Mass spectrum (FAB, Negative) m / e = 133
4 ([MH] ^- )

The coupler of the present invention may be used in any layer in a light-sensitive material, but it is not limited to a light-sensitive silver halide emulsion layer and / or a light-sensitive silver halide emulsion layer.
Alternatively, it is preferably added to a layer adjacent thereto, more preferably added to a light-sensitive silver halide emulsion layer, and particularly preferably added to a green-sensitive silver halide emulsion layer. The amount of these compounds added to the light-sensitive material is 3 × 10 ⁻⁷ when the leaving group X contains a photographically useful group component.
To 1 × 10 ⁻³ mol / m ² , preferably 3 × 10 ^{−6 to} 7
× 10 ^-4 mol / m ² , more preferably 1 × 10 ^-5 to 4 × 10
^-4 mol / m ² . When the leaving group X does not contain a photographically useful group component, the addition amount of the magenta dye-forming coupler is 3 × 10 ^{−5 to} 3 × 10 ⁻³ mol / m ² , and preferably It is 3 × 10 ^{−4 to} 2 × 10 ⁻³ mol / m ² , and more preferably 1 × 10 ^{−4 to} 1.5 × 10 ⁻³ mol / m ² .

In the present invention, preferably, a yellow dye-forming coupler (hereinafter referred to as a yellow coupler), a magenta dye-forming coupler (hereinafter referred to as a magenta coupler), and a cyan dye are used in the same manner as in a normal silver halide color photographic light-sensitive material. A forming coupler (hereinafter referred to as a cyan coupler) is used. In this case, the amount of the magenta coupler used is as described above, and the amount of the yellow or cyan coupler used is not particularly different from that of an ordinary silver halide color photographic light-sensitive material. The coupler of the present invention can be added in the same manner as a usual coupler as described later.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement in which a silver halide emulsion layer having a low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436, and JP-A-62-160448.
No. 63-89580, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 25 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles may also be large-sized particles having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
And No. 18716 (November 1979), 648.
Pp. 307105 (November 1989), 863.
~ 865, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Ph
otographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Chemistry (Focal Press, 196
6)), "Manufacturing and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4).

US Pat. Nos. 3,574,628 and 3,
Monodisperse emulsions described in, for example, 655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is formed on the surface as a seed, an internal latent image type in which the latent image is formed inside the grain, or a type in which a latent image is formed both on the surface and inside. It must be a negative emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are the above-mentioned Research Disclosure No. 17643, No. 18716 and No. 18716.
No. 307105, the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. What is a silver halide grain whose inside or surface is fogged?
It is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameters of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain is
It need not be optically sensitized, nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. The coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, and 4.5 or less.
Most preferred is g / m ² or less.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23 to 24 648 right column 866 to 868 Supersensitization Agent ~ page 649 right column 4 whitening agent page 24 647 page right column 868 page 5 antifoggant page 24 ~ 25 page 649 right column 868 ~ 870 page and stabilizer 6 light absorber, page 25 ~ 26 page 649 right column ~ Page 873 Filter dye page 650 Left column UV absorber 7 Anti-staining agent page 25 Right column page 650 Left column page 872 ~ Right column 8 Dye image stabilizer page 25 650 page left column 872 page 9 Hardener 26 page 651 page Left column 874 to 875 10 Binder page 26 Same as above 873 to 874 page 11 Plasticizer, lubricant 27 pages 650 page Right column 876 page 12 Coating aid, pages 26 to 27 Same as above 875 to 876 Surface active agent 13 Static protection 27 Page Same as above 876 to 877 Stop agent 14 Matting agent 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, the international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to incorporate the dyes described in No.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G, and No. 307105, VII-C. ~ G. Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,6.
No. 20, No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, Japanese Patent Publication No. 58-1
0739, British Patents 1,425,020, 1,476,760, U.S. Patent 3,973,968.
No. 4, No. 4,314, 023, No. 4,511, 64
Those described in No. 9, European Patent No. 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Patent (Publication) No. 3 , 234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No.
176-Section VII-G, No. 307105, VII-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, Item VII-F and Id. No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

The bleaching accelerator releasing couplers described in RD No. 11449, No. 24241, JP-A No. 61-201247 and the like are effective for shortening the time of the processing step having a bleaching ability. The effect is great when it is added to a light-sensitive material using silver halide grains.

As a coupler capable of releasing a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octylaniline, etc.) Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248 are used.
1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-described in JP-A No. 1-80941.
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, No. 18
716, right column, page 647 to left column, page 648, and No. 3 of the same.
07105, page 897. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, and 23 μm
The following is more preferable, and 18 μm or less is further preferable,
16 μm or less is particularly preferable. Also, the film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Phot) by A. Green et al.
Sci., Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is 30 in a color developing solution. 90% of the maximum swollen film thickness reached when treated at 3 ° C. for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150 to 500%
Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, No. 18;
No. 307, 651, left column to right column, and No. 307105, pages 880-881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic 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 their salts can be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0.1. It is 001-0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is
It is preferably applied not only in both the color development and black and white development steps but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing, stabilizing and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment may be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other amino acids. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH may be used for speeding up the processing. .

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 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 light-sensitive material for photographing.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, it is also preferable to use thiosulfate in combination with thiocyanate, thioether compound, thiourea and the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2 for adjusting the pH. It is preferable to add 0.1 to 10 mol / l of imidazoles such as methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-62-62.
The method of increasing the stirring effect by using the rotating means of No. 183461, and further, by moving the light-sensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent, the stirring effect is improved. There are a method of improving the method and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for processing the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
Nos. 8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes is selected. To be done. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such stabilizing treatment, JP-A-57-8543 and JP-A-5-543 have been used.
All the known methods described in JP-A-8-14834 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure No. 14850 and No. 15159, and aldol compounds described in No. 13924. The metal salt complexes described in U.S. Pat. No. 3,719,492 and the urethane compounds described in JP-A-53-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2 and the like.

[0155]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount was the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g / m for couplers, additives and gelatin.
Amounts expressed in m ² units and, for sensitizing dyes, the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple effects, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ⁻² Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10 ⁻² ExF-2 4.0 × 10 ⁻² ExF-3 5.0 × 10 ⁻³ Cpd -6 1.0 x 10 ^-3

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere-equivalent diameter 0.4 μm, variation coefficient of sphere-equivalent diameter 30%, plate-like grain , Diameter / thickness ratio 3.0) coated silver amount 0.35 silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.45 μm, sphere equivalent diameter Coefficient of variation 23%, plate-like particles, diameter / thickness ratio 2.0) Coating silver amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 0.09 ExC-2 4.0 × 10 ⁻² ExC-3 8.0 × 10 ⁻² ExC-5 0.08

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.65 μm, variation of sphere equivalent diameter) Coefficient 23%, plate-like particles, diameter / thickness ratio 2.0) Silver coating amount 0.80 Gelatin 1.46 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-52 .4 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 2.0 × 10 ^-2 ExC-3 0.10 ExC-5 0.19 ExC-6 2.0 X10 ^-2 ExM-3 2.0 x 10 ^-2 UV-2 5.7 x 10 ^-2 UV-3 5.7 x 10 ^-2

Fourth Layer (High-Sensitivity Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 9.3 mol%, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 24, 0, 6 mol from the inside) %, Equivalent sphere diameter 0.75 μm, coefficient of variation of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 2.5) Coating amount of silver 1.49 Gelatin 1.38 ExS-1 2.0 × 10 ⁻⁴ ExS-2 1.1x10 ^-4 ExS-5 1.9x10 ^-4 ExS-7 1.4x10 ^-5 ExC-1 8.0x10 ^-2 ExC-4 9.0x10 ^-2 ExC-6 2.0 × 10 ^-2 Solv-1 0.20 Solv-2 0.53

Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.33 μm, variation coefficient of sphere equivalent diameter 37%, plate-like particles , Diameter / thickness ratio 2.0) coating amount of silver 0.19 gelatin 0.44 ExS-3 1.5 × 10 ^-4 ExS-4 4.4 × 10 ^-4 ExS-5 9.2 × 10 ^-5 ExM -1 0.17 ExM-3 3.0x10 ^-2 Solv-1 0.13 Solv-4 1.0x10 ^-2

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 15%, plate-like particles , Diameter / thickness ratio 4.0) amount of coated silver 0.24 gelatin 0.54 ExS-3 2.1 × 10 ^-4 ExS-4 6.3 × 10 ^-4 ExS-5 1.3 × 10 ^-4 ExM -1 0.15 ExM-3 4.0 x 10 ^-2 ExY-1 3.0 x 10 ^-2 Solv-1 0.13 Solv-4 1.0 x 10 ^-2

Eighth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.8 mol%, multi-structured grains having a silver amount ratio 3: 4: 2, AgI content of 24, 0, 3 from the inside). Mol%, sphere equivalent diameter 0.75 μm, variation coefficient of sphere equivalent diameter 23%, plate-like particles, diameter / thickness ratio 1.6) Coating amount of silver 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^{− 4} ExS-5 8.6 × 10 ⁻⁵ ExS-8 2.8 × 10 ⁻⁵ ExM-2 2.0 × 10 ⁻² ExM-5 2.0 × 10 ⁻² ExM-6 6.0 × 10 ^{− 2} ExY-1 3.0 × 10 ^-2 ExC-1 0.8 × 10 ^-2 ExC-4 0.5 × 10 ^-2 ExC-6 1.0 × 10 ^-2 Solv-1 0.23 Solv-2 5.0 x 10 ^-2 Solv-4 1.0 x 10 ^-2 Cpd-8 1.0 x 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2

Tenth Layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.65 μm, sphere equivalent) Coefficient of variation of diameter 25%, tabular grains, diameter / thickness ratio 2.0) Coating amount 0.67 Silver iodobromide emulsion (AgI 4.0 mol%, core-shell ratio 1: 3, internal high AgI type, sphere) Equivalent diameter 0.4 μm, variation coefficient of spherical equivalent diameter 15%, normal crystal grains) Coating silver amount 0.20 Gelatin 0.87 ExS-3 6.7 × 10 ⁻⁴ ExM-4 0.16 Solv-10. 30 Solv-6 3.0 x 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ⁻² gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 8.0 × 10 ⁻² Cpd-6 2.0 x 10 ^-3 H-1 0.25

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grains , Diameter / thickness ratio 7.0) coating silver amount 0.50 silver iodobromide emulsion (AgI 3.0 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 30%, plate-like Grain, diameter / thickness ratio 7.0) Coating silver amount 0.30 Gelatin 2.18 ExS-6 9.0 × 10 ^-4 ExC-1 0.05 ExC-2 0.10 ExY-2 0.05 ExY- 3 1.09 Solv-1 0.54

Thirteenth Layer (Intermediate Layer) Gelatin 0.40 ExY-4 0.19 Solv-1 0.19

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, multiple pairs Crystal plate particles, diameter / thickness ratio 2.0) Coating amount of silver 0.40 Gelatin 0.49 ExS-6 2.6 × 10 ⁻⁴ ExY-2 1.0 × 10 ⁻² ExY-3 0.20 ExC -1 1.0 x 10 ^-2 Solv-1 9.0 x 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating amount of silver 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ⁻² Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ⁻²

Sixteenth Layer (Second Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.85 B-1 (Diameter 1.5 μm) 8.0 × 10 ^-2 B-2 (diameter 1.5 μm) 8.0 × 10 ^-2 B-3 2.0 × 10 ^-2 W-4 2.0 × 10 ^-2 H -1 0.18

In addition to the above, the samples prepared in this way were
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. Furthermore, B-4, B-5, F-1, F-2, F-3,
F-4, F-5, F-6, F-7, F-8, F-9, F
-10, F-11, F-12 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

In addition to the above components, each layer contains a surfactant W.
-1, W-2, and W-3 were added as a coating aid or an emulsifying dispersant.

[0176]

[Chemical 36]

[0177]

[Chemical 37]

[0178]

[Chemical 38]

[0179]

[Chemical Formula 39]

[0180]

[Chemical 40]

[0181]

[Chemical 41]

[0182]

[Chemical 42]

[0183]

[Chemical 43]

[0184]

[Chemical 44]

[0185]

[Chemical 45]

[0186]

[Chemical 46]

[0187]

[Chemical 47]

[0188]

[Chemical 48]

[0189]

[Chemical 49]

[0190]

[Chemical 50]

[0191]

[Chemical 51]

[0192]

[Chemical 52]

[0193]

[Chemical 53]

[0194]

[Chemical 54]

(Samples 102 to 110) First of Sample 101
Samples 102 to 110 were prepared in the same manner as Sample 101, except that the compound ExM-4 in Layer 0 was changed as shown in Table 1.

After subjecting the obtained samples 101 to 110 to white imagewise exposure, color was measured using an automatic processor in the following manner (until the cumulative replenishment amount of the solution became 3 times the capacity of the mother liquor tank). Development processing was performed.

Treatment method Process treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C. 33 ml 20 liters Bleach 6 minutes 30 seconds 38 ° C. 25 ml 40 liters Water washing 2 minutes 10 seconds 24 ° C. 1200 ml 20 liters Fixed 4 Minutes 20 seconds 38 ℃ 25ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ 10 liters from (2) to (1) Countercurrent piping water wash (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liters stable 1 minute 05 seconds 38 ° C 25ml 10 liters Dry 4 minutes 20 seconds 55 ° C Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid is shown. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2 -Methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleach) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 10.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Water was added to 1.0 liter 1.0 liter pH 6.0 5.7

(Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Aqueous ammonium thiosulfate solution (70 %) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6

(Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediamine tetra Acetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0

Table 1 shows the MTF value of the magenta image of 25 cycles / mm of the obtained sample. The MTF value is measured by The Theory of the Photographic Process, 3rd e
The method described in d. (Macmillan, published by Mies) was followed. Further, the value obtained by subtracting the yellow density in the magenta fog density from the yellow density at the exposure amount giving the magenta density (fog +1.2) after the uniform blue exposure is given to the green imagewise exposure is the color turbidity (ΔD). _B ) is shown in Table 1.

Further, two sheets of the same sample were simultaneously exposed in a white imagewise manner, and one sheet was stored in a freezer under the condition of 50 ° C. and 80% relative humidity for 7 days. Then, the sensitivity change at the magenta density (fog + 0.5) was read, and the result was shown in Table 1 as the sensible material storage stability (ΔS _0.5 ).
It was shown to. Sensitivity change here is density (fog + 0.5)
The exposure dose that gives
_It was expressed as logE ₀ −logE ₁ when ₀ and E ₁ .

Further, the sample after the development processing was processed with a fluorescent lamp 2000.
Stored at the conditions of irradiation 0Lux 7 days, reads the density variation in terms of the magenta density (fog + 1.0) are shown in Table 1 combined as light fastness ([Delta] D _G).

[0205]

[Table 1]

As is clear from Table 1, the samples using the compounds of the present invention are excellent in sharpness represented by MTF value and color reproducibility represented by color turbidity. Further, it can be seen that the samples of the present invention are more excellent in storability of the light-sensitive material, and particularly the light fastness is remarkably improved.

Example 2 In this example, the effect of using the compound of the present invention as a magenta coupler will be shown.

(Sample 201) Half of the compound ExM-1 in the seventh layer of Sample 101 was added to an equal amount of ExM-6, and the compound ExM-5 in the eighth layer was added to 1.0 × 10 ^-2 g / m ^2. ExM
Sample 2 was prepared in the same manner as Sample 101 except that it was replaced with -6.
01 was produced.

(Samples 202 to 209) Seventh Sample 201
Samples 202 to 209 in the same manner as Sample 201, except that the compound ExM-6 of the layer and the eighth layer was changed as shown in Table 2.
Was produced.

In accordance with Example 1, the color turbidity (ΔD _B ) of the obtained sample, the storability of the photosensitive material (ΔS _0.5 ), and the light fastness (ΔD)
_G ) was obtained and is shown in Table 2. In addition, regarding the sample which was subjected to the development processing after being exposed to the green imagewise exposure, the relative humidity at 80 ° C. was 7
The degree of change in hue (Δλmax) was measured by measuring the change value (nm) of the maximum absorption wavelength of magenta when stored for 3 days under the condition of 0%.
Is shown in Table 2.

[0211]

[Table 2]

As is clear from Table 2, the sample using the compound of the present invention is excellent in color reproducibility represented by the degree of color turbidity and storage stability of the light-sensitive material. In particular, the sample containing the compound in which the leaving group is an azolyl group is more excellent in storability of the photosensitive material. Furthermore, it can be seen that the samples of the present invention have improved light fastness and that the change in hue due to dye aggregation after treatment is also small.

Example 3 On a subbed cellulose triacetate film support,
A sample 301, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount was the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g / m for couplers, additives and gelatin.
Amounts expressed in m ² units and, for sensitizing dyes, the number of moles per mole of silver halide in the same layer.

First Layer: Antihalation Layer Black Colloidal Silver Silver Coating Amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1. 9 x 10 ^-2 Solv-1 0.30 Solv-2 1.2 x 10 ^-2

Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, sphere equivalent diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ⁻² Cpd -3 2.0 x 10 ^-2

Third Layer: First Red Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high Agl type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular grains , Diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl type, spherical equivalent diameter 0.4 μm, variation coefficient of spherical equivalent diameter 18%, 10 Tetrahedral grains) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC- 1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32

Fourth Layer: Second Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Agl type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles , Diameter / thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ⁻⁴ mol ExS-2 1.0 × 10 ⁻⁴ mol ExS-3 3.0 × 10 ^{− 5} mols ExC-1 0.13 ExC-2 6.2x10 ^-2 ExC-4 4.0x10 ^-2 ExC-6 3.0x10 ^-2 Solv-1 0.10.

Fifth Layer: Third Red-Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high Agl type, sphere equivalent diameter 1.4 μm, variation coefficient of sphere equivalent diameter 28%, plate-like particles , Diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ⁻⁴ mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ^{− 5} mols ExC-2 5.0 × 10 ^-2 ExC-5 7.3 × 10 ^-2 ExC-6 1.0 × 10 ^-2 ExC-7 4.0 × 10 ^-2 Solv-1 0.12 Solv- 2 0.12

Sixth Layer (Intermediate Layer) Gelatin 1.00 Cpd-4 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Seventh Layer: First Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high Agl type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular grains , Diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high Agl type, spherical equivalent diameter 0.4 μm, variation coefficient of spherical equivalent diameter 18%, 10 Tetrahedral grains) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.0 × 10 ^-4 mol ExS-5 2.0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM- 1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 Solv-1 0.20 Solv-3 3.0 × 10 ^-2

Eighth Layer: Second Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Agl type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles , Diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ⁻⁴ mol ExS-5 1.4 × 10 ⁻⁴ mol ExS-6 7.0 × 10 ^{− 5} mol ExM-1 0.12 ExM-2 9.0x10 ^-3 ExM-3 3.5x10 ^-2 Solv-1 0.15 Solv-3 1.0x10 ^-2

Ninth layer: intermediate layer gelatin 0.50 Solv-1 2.0 × 10 ^-2

Tenth Layer: Third Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 11.3 mol%, internal high Agl type, sphere equivalent diameter 1.4 μm, variation coefficient of sphere equivalent diameter 28%, plate-like grain , Diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ⁻⁴ mol ExS-5 8.0 × 10 ⁻⁵ mol ExS-6 8.0 × 10 ^{− 5} mol ^{ExM-4 5.8 × 10 -2 ExM} -6 5.0 × 10 -3 ExC-2 4.5 × 10 -3 Cpd-5 1.0 × 10 -2 Solv-1 0.25

Eleventh layer: Yellow filter layer Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12

Twelfth layer: intermediate layer Gelatin 0.45 Cpd-3 0.10.

Thirteenth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 25%, tabular grain, diameter / Thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ⁻⁴ mol ExY-1 0.60 ExY-2 2.3 × 10 ⁻² Solv-1 0.15

14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal height Ag1 type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 16%, octahedral grains ) Silver coating amount 0.19 Gelatin 0.35 ExS-7 2.0x10 ^-4 mol ExY-1 0.22 ExY-3 1.0x10 ^-3 Solv-1 7.0x10 ^-2

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform Agl type, sphere equivalent diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

Sixteenth Layer: Third Blue Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, spherical equivalent diameter 1.7 μm, variation coefficient of spherical equivalent diameter 28%, plate-like particles , Diameter / thickness ratio 5.0) Silver coating amount 1.40 Gelatin 1.00 ExS-8 1.5x10 ^-4 mol ExY-1 0.21 Solv-1 7.0x10 ^-2 17th layer: First protective layer Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2

Eighteenth layer: Second protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.70 B-1 (diameter 1.5 μm) 2.0 × 10 ^-2 B- 2 (diameter 1.5 μm) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

In addition to the above, the sample thus prepared
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. Furthermore, B-4, B-5, W-2, W-3, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F
-8, F-9, F-10, F-11, F-12, F-1
3 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt.

[0233]

[Chemical 55]

[0234]

[Chemical 56]

[0235]

[Chemical 57]

[0236]

[Chemical 58]

[0237]

[Chemical 59]

[0238]

[Chemical 60]

[0239]

[Chemical formula 61]

[0240]

[Chemical formula 62]

[0241]

[Chemical 63]

[0242]

[Chemical 64]

[0243]

[Chemical 65]

[0244]

[Chemical 66]

[0245]

[Chemical 67]

[0246]

[Chemical 68]

[0247]

[Chemical 69]

[0248]

[Chemical 70]

[0249]

[Chemical 71]

[0250]

[Chemical 72]

(Samples 302 to 310) Seventh Sample 301
Samples 302 to 310 were prepared in the same manner as Sample 301 except that the compound ExM-2 of the first layer and the eighth layer was changed as shown in Table 3.
Was produced.

According to Example 1, the color turbidity (ΔD _B ) of the obtained sample, the storability of the photosensitive material (ΔS _0.5 ), and the light fastness (ΔD)
_G ) was obtained and is shown in Table 3. Table 3 also shows the RMS values at the density of magenta density (fog + 1.0) measured with an aperture having a diameter of 48 μm.

However, the color development processing was carried out by the following processing steps and processing liquid compositions. Processing method Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C 25 ml 10 liters Bleach 45 seconds 38 ° C 5ml 4 liters Settling (1) 45 seconds 38 ° C-4 liters Settling (2) 45 seconds 38 ℃ 30ml 4 liters Water wash (1) 20 seconds 38 ℃ -2 liters Water wash (2) 20 seconds 38 ℃ 30ml 2 liters Stability 20 seconds 38 ℃ 20ml 2 liters Dry 1 minute 55 ℃ Replenishment amount is 35mm Amount per 1 m width The bleach-fixing and washing steps are countercurrent systems from (2) to (1), and the overflow of the bleaching solution is all introduced into the bleach-fixing (2). In the above processing, the amount of the bleach-fixing solution brought into the washing step was 35 mm wide for the photosensitive material 1.
It was 2 ml per m length.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0. 5 Potassium iodide 1.2 mg-Hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.7 4.2 Add water 1.0 liter 1.0 liter pH 10.00 10.15

(Bleaching solution) Mother liquor (g) Replenishing solution (g) 1,3-Diaminopropane tetraacetic acid Ferric ammonium monohydrate 144.0 206.0 1,3-Diaminopropane tetraacetic acid 2.8 4. 0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Water was added to 1.0 liter 1.0 liter pH 4 .3 3.4

(Bleach-fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 25.0 Ammonium sulfite 12.0 20. 0 Aqueous ammonium thiosulfate solution (70 g / l) 290.0 ml 320.0 ml Ammonia water (27%) 6.0 ml 15.0 ml Water was added to 1.0 liter 1.0 liter pH 6.8 8.0

(Washing water) Common to mother liquor and replenisher The tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IRA-). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by 20 m of sodium diisocyanurate dichloride.
g / l and 150 mg / l sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 1.2 ml Surfactant [C ₁₀ H ₂₁ —O— (CH ₂ CH ₂ O) ₁₀ —H] 0.4 Ethylene Glycol 1.0 Add water 1.0 liter pH 7.0-7.0

[0259]

[Table 3]

As is clear from Table 3, the samples using the compound of the present invention are excellent in graininess represented by RMS value and color reproducibility represented by color turbidity. Further, it can be seen that the sample of the present invention is excellent in storability of the light-sensitive material, and the light fastness after processing is remarkably improved.

[0261]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention is excellent in color reproducibility by improving sharpness, graininess and multi-layer effect, and is also particularly excellent in storability of a photographic material and color image stability after processing. ing.

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material containing a coupler represented by the following general formula (I). [Chemical 1] (In the formula, R ₁ represents a methyl group to which a substituent linked by at least one oxygen atom, nitrogen atom or sulfur atom, a halogen atom, an acyl group, a cyano group or a nitromethyl group is bonded, and R ₂ is an aliphatic group or Represents an aromatic group, R
₃ represents a hydrogen atom, an aliphatic group or an aromatic group. Z ₁
And Z ₂ each represent a nitrogen atom or = C (R ₄ )-, and when Z ₁ and Z ₂ are both = C (R ₄ )-, 2
The two R _{4 s} may be the same or different. R ₄ is a hydrogen atom, halogen atom, aliphatic group, aryl group, heterocyclic group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, sulfonyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, amide group, alkoxycarbonyl It represents an amino group, a ureido group, a sulfonamide group, a sulfamoylamino group, an azo group, a nitro group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfinyl group, a sulfonyl group, a sulfamoyl group, a sulfo group and a phosphinyl group. Here, any of R _{1 to} R ₄ may be a divalent group to form a bis form. X represents a hydrogen atom or a coupling-off group. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein X is a development inhibitor residue. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein X is an azolyl group which is not a development inhibitor residue. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein X is a substituted or unsubstituted pyrazolyl group.