JPH0659410A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sensitivity and storage stability with the lapse of time in the silver halide color photographic sensitive material and to enhance color image fastness, color turbidity, sharpness, and desilverability of the color photosensitive material. CONSTITUTION:The silver halide color photographic sensitive material contains a compound for releasing the precursor of a development inhibitor represented by formula I in which A is a group to be allowed to release X and to produce a soluble or decoloring compound in a processing solution by reaction with the oxidation product of a developing agent, and X is the precursor of the development inhibitor, and it also contains an oil-soluble dye represented by formula II in which each of X and Y is an electron-attractive group or a 5- or 6-membered ring obtained by combining them; Ar is an aromatic hetero ring, such as indole, furan, thiophene, coumarin, or pyridine; each of L<1>-L<3> is a methine group; and n is 0, 1, or 2.

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, which has particularly high sensitivity and high image quality.
The present invention relates to a silver halide color photographic light-sensitive material excellent in storability and color image fastness of the light-sensitive material.

[0002]

2. Description of the Related Art Regarding the compound releasing a precursor of a development inhibitor according to the present invention, for example, JP-A-58-16095.
No. 4, No. 58-162949, No. 61-156127.
No. 63-37350, Journal of the Photographic Society of Japan, Volume 52 (1
1989) No. 2, pp. 150-155 (Kida, et al.) Or 1989 Annual Meeting of the Photographic Society of Japan, 2A0-22
(Kida) has a copy. However, when these compounds are used in a usual manner, a development-inhibiting compound is finally released, and although the image quality such as color reproducibility and graininess is improved, the sensitivity of photographic properties is lowered and it is difficult to increase the sensitivity of the light-sensitive material. Make something Therefore, the usage method and usage amount are limited. Further, the above-mentioned compounds are not satisfactory in the effect of improving the image quality, and further improvement has been desired, and further improvement in the storage stability and color image fastness of the light-sensitive material has been strongly desired.

On the other hand, regarding the dyes used in the light-sensitive material, for example, a filter layer for controlling the spectral composition of light incident on the photosensitive layer, a dye for a halation prevention layer for preventing light scattering, or an anti-irradiation dye. Used as. The dye used for the above purpose must satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) Photochemically inactive. In other words, it should not adversely affect the performance of the silver halide emulsion in a chemical sense, such as reduction in sensitivity, latent image regression or fog. (3) In the color development processing process, it should be decolorized, dissolved and removed so as not to leave unnecessary coloring on the processed light-sensitive material.

Many efforts have been made to find dyes satisfying these conditions, and some dyes have been proposed. Regarding the dyes relating to the present invention, for example, dyes similar to those disclosed in JP-A-3-167546 and JP-A-3-144438 are disclosed. However, it cannot be said that the dyes described in the above-mentioned published patents are photochemically inactive as described in (2) above, and when the light-sensitive material is stored with time, fog increases and sensitivity decreases. I found that there was a problem. It was also found that the decolorizing property is not sufficient, and there are problems such as residual color and deterioration of color image fastness.

[0005]

Therefore, the first object of the present invention is to provide a highly sensitive silver halide color photographic light-sensitive material. The second object is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility. A third object is to provide a silver halide color photographic light-sensitive material excellent in stability over time of the light-sensitive material. Fourth of purpose
Is to provide a silver halide color photographic light-sensitive material having good color image fastness.

[0006]

The above-mentioned object can be achieved by the silver halide color photographic light-sensitive material described below. (1) It has at least one photosensitive silver halide emulsion layer on a support, contains a precursor releasing compound of a development inhibitor represented by the following general formula (I), and is represented by the following chemical formula 4. A silver halide color photographic light-sensitive material containing an oil-soluble dye represented by the general formula (A). Formula (I) AX In the formula, A represents a group which reacts with an oxidized product of a developing agent to release X and forms a compound soluble or decolorizable in a processing solution, and X represents a precursor of a development inhibitor. Represents a body residue. General formula (A)

[0007]

[Chemical 4]

In the formula, X and Y each represent an electron-withdrawing group or a 5- or 6-membered ring in which X and Y are bonded,
Ar represents a heteroaromatic ring of indole, furan, thiophene, coumarin or pyridine, L ¹ , L ² and L ³ each represent a methine group, and n represents 0, 1 or 2.

(2) A halogenated compound according to the above (1), which comprises a coupler represented by the general formula (II) represented by the following chemical formula 5 or the general formula (III) represented by the following chemical formula 6. Silver color photographic light-sensitive material. General formula (II)

[0010]

[Chemical 5]

In the formula, R ₁ is --CONR ₄ R ₅ , --SO _{2
NR 4 R 5, -NHCOR 4,} -NHCOOR 6, -N
HSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHSO
₂ NR ₄ R ₅ , R ₂ is a group capable of substituting on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, and X is a hydrogen atom or an aromatic primary amine developer oxidant. Represents a group capable of leaving by a coupling reaction with. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{2 s} may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring. In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III)

[0012]

[Chemical 6]

In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group.

(3) The above-mentioned (1) or (2), wherein the amount of gelatin coated in the layer containing the oil-soluble dye represented by the general formula (A) is 1.5 g / m ² or less. Silver halide color photographic light-sensitive material.

The present invention will be described in detail below. First, the precursor releasing compound of the development inhibitor represented by the general formula (I) of the present invention will be described. The compound represented by the general formula (I) of the present invention is specifically described by the following general formula (I
It is represented by a) and the general formula (Ib).

General formula (Ia) A- (TIME) _a -DI General formula (Ib) A- (TIME) _i -RED-D
In the formula, A is (TIME) _a -DI or (T) by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.
IME) represents a coupler residue that leaves an _i- RED-DI and produces an alkali-soluble compound.
ME leaves DI from A by coupling reaction and then DI
Or represents a timing group that cleaves RED-DI, R
ED represents a group that cleaves DI by reacting with an oxidized product of a developing agent after leaving from A or TIME, DI represents a development inhibitor, a represents 1 or 2, and i represents 0 or 1. When a is 2, two TIMEs represent the same or different.

The coupler residue represented by A will be described below. When A represents a yellow coupler residue, for example, pivaloyl acetanilide type, benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, benzoxazoli Luacetamide type, benzimidazolyl acetamide type,
Examples thereof include quinazolin-4-one-2-ylacetanilide type or cycloalkanoylacetamide type coupler residues. When A represents a magenta coupler residue, for example, 5-pyrazolone type, pyrazolo [1,5-a] benzimidazole type, pyrazolo [1,5-b] [1,2,
4] triazole type, pyrazolo [5,1-c] [1,
2,4] triazole type, imidazo [1,2-b] pyrazole type, pyrrolo [1,2-b] [1,2,4] triazole type, pyrazolo [1,5-b] pyrazole type or cyanoacetophenone type Coupler residue.
When A represents a cyan coupler residue, examples thereof include phenol type, naphthol type and 2,4-diphenylimidazole type. Further, A may be a phenyl residue that leaves substantially no color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues.

A preferred example of A is the following general formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), a coupler residue represented by (Cp-9) or (Cp-10). These couplers are preferred because of their high coupling speed.

[0019]

[Chemical 7]

[0020]

[Chemical 8]

The free bond derived from the coupling position in the above formula represents the bonding position of the coupling leaving group. In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ ,
R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃
The number of carbon atoms in each is preferably 10 or less. The coupler residue represented by A is -COOR ₇₁ , -SO ₃ H, -O.
It is preferred to have at least one of H, -CONHR ₇₂ or -SO ₂ NHR ₇₂ as a substituent. That is, in the general formula (Cp-1), at least one of R ₅₁ or R ₅₂ and in the general formula (Cp-2), at least one of R ₅₁ , R _52, or R ₅₃ is represented by the general formula (Cp- In 3), at least one of R _{54 and} R ₅₅ is represented by the general formula (C
R ₅₆ or R _{57 in} p-4) and (Cp-5)
Is at least one of R in the general formula (Cp-6).
_At least one of _{58 and} R ₅₉ has the general formula (Cp-7).
In the formula (Cp-8), at least one of R ₅₉ or R ₆₀ is at least 1 of R ₆₁ or R ₆₂ .
In the general formulas (Cp-9) and (Cp-10), at least one R ₆₃ is —COOR ₇₁ , —SO ₃
It is preferable to have at least one of H, —OH, —CONHR ₇₂ or —SO ₂ NHR ₇₂ as a substituent. R ₇₁
Represents a hydrogen atom, an alkyl group having 6 or less carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl) and a phenyl group, and these may further have a substituent. R ₇₂ is a group represented by R ₇₁ , an acyl group (eg, acetyl, propionyl, butyryl, trifluoroacetyl) or a sulfonyl group (eg, methanesulfonyl, butanesulfonyl, benzenesulfonyl,
p-chlorobenzenesulfonyl, p-nitrobenzenesulfonyl).

R _{51 to} R ₆₃ , b, d and e will be described in detail below. In the following, R ₄₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₃ . b represents 0 or 1. R ₅₄ is R
₄₁ the same meanings of the _{group, R 41 CON (R 43)} - group, R ₄₁ SO
₂ N (R ₄₃ ) -groups, R ₄₁ N (R ₄₃ ) -groups, R ₄₁ S-groups,
It represents an R ₄₃ O-group or an R ₄₅ N (R ₄₃ ) CON (R ₄₄ ) -group. R ₅₅ has the same meaning as R ₄₁ . R ₅₆ and R ₅₇ are each a group having the same meaning as R ₄₃ , R ₄₁ S-group, and R ₄₃
O-group, R ₄₁ CON (R ₄₃ ) -group, or R ₄₁ SO ₂ N
Represents an ( _R43 )-group. R ₅₈ has the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43)
-Group, R ₄₁ OCON (R ₄₃ ) -group, R ₄₁ SO ₂ N
(R ₄₃ ) -group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) -group, R
₄₁ O- group, R ₄₁ S- group, halogen atom, or R ₄₁ N
Represents an (R ₄₃ ) -group. d represents 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents. R ₆₀ has the same meaning as R ₄₁ . R ₆₁
Represents a group having the same meaning as R ₄₃ . R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁ S
O ₂ NH- _{group, R 43 N (R 44)} CONH- group, R ₄₃ N
(R ₄₄₎ SO ₂ NH- group, R ₄₃ O-group, R ₄₁ S- group, a halogen atom or R ₄₁ NH- group. R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R ₄₄ ) -group, R ₄₃ N
(R ₄₄₎ CO- _{group, R 41 SO 2 N (R} 43) - group, R ₄₃ N
(R ₄₄₎ SO ₂ - group, R ₄₁ SO ₂ - group, R ₄₃ OCO-
Represents a group, R ₄₃ O—SO ₂ — group, halogen atom, nitro group, cyano group or R ₄₃ CO— group. e represents an integer of 0 to 4. When a plurality of R ₆₂ or R ₆₃ are present, they represent the same or different.

In the above, the alkyl group has 1 to 3 carbon atoms.
2, preferably 1 to 20 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted alkyl groups. As typical examples, methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-
Examples include ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-decyl. The aryl group is a substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl having 6 to 20 carbon atoms.
The heterocyclic group is a heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 selected from nitrogen atom, oxygen atom or sulfur atom. It is preferably a substituted or unsubstituted heterocyclic group having a 3- to 8-membered ring. Typical examples of the heterocyclic group are 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-
Indolyl, 1,3,4-thiadiazol-2-yl,
A 1,2,4-triazol-2-yl group or 1-indolinyl may be mentioned.

When the alkyl group, aryl group and heterocyclic group have a substituent, typical substituents are a halogen atom, R ₄₇ O- group, R ₄₆ S- group and R ₄₇ CON.
(R ₄₈₎ - _{group, R 47 N (R 48)} CO- group, R ₄₆ OCON
(R ₄₇ ) -group, R ₄₆ SO ₂ N (R ₄₇ ) -group, R ₄₇ N (R
₄₈₎ SO ₂ - radical, R ₄₆ SO ₂ - radical, R ₄₇ OCO- radical, R
₄₇ N (R ₄₉ ) CON (R ₄₈ )-group, R ₄₇ CONHSO ₂
- group, R ₄₇ NHCONHSO ₂ - group, a group having the same meaning as _{R 46, R 47 N (R} 48) - group, R ₄₆ COO- groups, R ₄₇ OSO
_{A 2} -group, a cyano group or a nitro group can be mentioned. Here, R ₄₆ represents an alkyl group, an aryl group, or a heterocyclic group, and R ₄₇ , R _48, and R ₄₉ each represent an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined.

Next, preferred ranges of R _{51 to} R ₆₃ , b, d and e will be described. R ₅₁ is preferably an alkyl group, an aryl group or a heterocyclic group. R ₅₂ and R ₅₅ are preferably aryl groups. R ₅₃ is preferably an aryl group when b is 1 and a heterocyclic group when b is 0. R ₅₄ is R ₄₁ CONH-
A group, or R ₄₁ N (R ₄₃ ) -group is preferred. R ₅₆ and R ₅₇ are preferably an alkyl group, R ₄₁ O— group, or R ₄₁ S— group. R ₅₈ is preferably an alkyl group or an aryl group. In the general formula (Cp-6), R ₅₉ is a chloro atom,
Alkyl group or R ₄₁ CONH-group is preferable, and d is 1
Or 2 is preferable. R ₆₀ is preferably an aryl group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group, and d is preferably 1. R ₆₁ is preferably an alkyl group or an aryl group. In general formula (Cp-8), e is preferably 0 or 1. R ₆₂ is R ₄₁ OCONH-
Group, R ₄₁ CONH-group or R ₄₁ SO ₂ NH-group is preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ CO
NH-group, R ₄₁ SO ₂ NH-group, R ₄₁ N (R ₄₃ ) SO ₂
- group, R ₄₁ SO ₂ - _{group, R 41 N (R 43)} CO- group, a nitro group or a cyano group are preferable, e is 1 or 2 are preferred. In the general formula (Cp-10), R ₆₃ is R ₄₃ NCO.
- group, R ₄₃ OCO- group or R ₄₃ CO- group are preferred,
e is preferably 1 or 2.

Next, the development inhibitor represented by DI will be described. Examples of the development inhibitor represented by DI include Research Disclosure 7
Volume 6, No. 17643, (December 1978), U.S. Pat. Nos. 4,477,563, 5021332, 502.
No. 6628, No. 3227554, No. 3384657
No. 3615506, No. 3617291, No. 37
No. 33201, No. 3933500, No. 39598993
Nos. 3961959, 4149886, 42
59437, 4095984, 4782012
No., British Patent No. 1450479 or US Patent No. 50
Development inhibitors such as those described in 34311 are included. Preferably, heterocyclic thio group, heterocyclic seleno group or triazolyl group (monocyclic or condensed ring 1, 2, 3
-Triazolyl or 1,2,4-triazolyl), particularly preferably tetrazolylthio, tetrazolylseleno, 1,3,4-oxadiazolylthio, 1,3,3.
4-thiadiazolylthio, 1- (or 2-) benzotriazolyl, 1,2,4-triazol-1- (or 4-) yl, 1,2,3-triazol-1-yl, 2
-Benzothiazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio and derivatives thereof. A preferred development inhibitor is represented by the following general formula DI-1.
~ DI-6.

[0027]

[Chemical 9]

In the formula, R ₁₁ is a halogen atom (for example, a bromine atom or a chlorine atom), an alkoxycarbonyl group (having 2 carbon atoms).
-20, preferably 2-10. For example, methoxycarbonyl, isoamyloxycarbonylmethoxycarbonyl), an acylamino group (having 2 to 20 carbon atoms, preferably 2 carbon atoms)
~ 10. For example, hexanamide, benzamide), a carbamoyl group (having 1 to 20 carbon atoms, preferably 1 to 10. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl), a sulfamoyl group (having 0 to 20 carbon atoms, Preferably 1 to 10. For example, N-butylsulfamoyl), an alkoxy group (having 1 to 2 carbon atoms).
0, preferably 1-10. For example, methoxy, benzyloxy), aryloxy group (C6-10, preferably 6-10. For example, phenoxy, 4-methoxyphenoxy, naphthoxy), aryloxycarbonyl group (C7-21, preferably 7-11). . For example, phenoxycarbonyl), alkoxycarbonylamino groups (2 carbon atoms)
-20, preferably 2-10. For example, ethoxycarbonylamino), cyano group, nitro group, alkylthio group (having 1 to 20 carbon atoms, preferably 1 to 10; methylthio, hexylthio), ureido group (having 1 to 20 carbon atoms, preferably 1 to 10. For example, N. -Phenylureido), an aryl group (having 6 to 10 carbon atoms, for example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 1 carbon atoms).
0. A monocyclic or condensed ring having 3 to 12, preferably a 5- or 6-membered ring containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. For example, 2-pyridyl, 1-pyrrolyl, morpholino, indolyl), alkyl group (having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms)
0, straight-chain, branched, cyclic, saturated, unsaturated. For example, methyl, ethyl, butoxycarbonylmethyl, 4-methoxybenzyl, benzyl), an acyl group (having 1 to 20 carbon atoms, preferably 2 to 10; for example, acetyl, benzoyl), an arylthio group (having 6 to 10 carbon atoms, preferably 6 carbon atoms). ~ 10.
For example, phenylthio, naphthylthio), or an aryloxycarbonylamino group (having 7 to 11 carbon atoms, for example, phenoxycarbonylamino). The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here. In the formula, R ₁₂ is an aryl group (having 6 to 10 carbon atoms, for example, phenyl, naphthyl, 4-methoxyphenyl, 3-methoxycarbonylphenyl),
Heterocyclic group (having 1 to 10 carbon atoms. As a hetero atom, for example, at least one nitrogen atom, at least one oxygen atom, or at least one sulfur atom is a 3 to 12, preferably a 5- or 6-membered, monocyclic or condensed ring. For example, 2-pyridyl. , 1-pyrrolyl,
Morpholino, indolyl), or an alkyl group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, straight-chain, branched, cyclic,
Saturated or unsaturated. For example, methyl, ethyl, butoxycarbonylmethyl, 4-methoxybenzyl, benzyl). f is 1 to 4, g is 0 or 1, and h is 1 or 2. V represents an oxygen atom, a sulfur atom or -N (R ₄₁ )-, and R ₄₁ has the same meaning as previously defined.

Next, the group represented by TIME will be described. The group represented by TIME may be any linking group capable of cleaving DI after cleaving from A during development processing. For example, groups utilizing the cleavage reaction of hemiacetal described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297, U.S. Pat. Nos. 4,248,962, 4,847,185 or 485.
A timing group for causing a cleavage reaction utilizing an intramolecular nucleophilic substitution reaction described in 7440, US Pat. No. 440.
No. 9323 or No. 4421845, a timing group that causes a cleavage reaction by utilizing an electron transfer reaction, a group that causes a cleavage reaction by utilizing a hydrolysis reaction of an iminoketal described in US Pat. No. 4,546,073, Alternatively, a group capable of causing a cleavage reaction by utilizing a hydrolysis reaction of an ester described in West German Laid-Open Patent No. 2626317 can be mentioned. TIME binds to A at a heteroatom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom. Preferred TIME includes the following general formula (T-1), (T-2) or (T-3). General formula (T-1) *-W- (X = Y) _j- C
(R ₂₁ ) R ₂₂ -** General formula (T-2) * -W-CO-** General formula (T-3) * -W-LINK-E-** In the formula, * represents the general formula (Ia ) And in the general formula (Ib) represent a position to be bonded to A, and ** represents DI in the general formula (Ia).
Alternatively, the position of bonding to TIME (when a is plural) represents the position of bonding to RED in the general formula (Ib), W represents an oxygen atom, a sulfur atom or> N—R ₂₃ , and X and Y are respectively Represents a methine or nitrogen atom, j represents 0, 1 or 2, and R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a substituent. Here, when X and Y represent a substituted methine, the substituent and any two substituents of R ₂₁ , R ₂₂ and R ₂₃ are linked to form a cyclic structure (for example, a benzene ring or a pyrazole ring). Or it may not be formed. In the general formula (T-3), E represents an electrophilic group, and LINK represents a linking group sterically related to each other so that W and E can undergo an intramolecular nucleophilic substitution reaction. Specific examples of TIME represented by the general formula (T-1) are as follows.

[0030]

[Chemical 10]

Specific examples of TIME represented by the general formula (T-2) are as follows.

[0032]

[Chemical 11]

Specific examples of TIME represented by the general formula (T-3) are as follows.

[0034]

[Chemical 12]

Specific examples of (TIME) _a when a is 2 or more in the general formula (Ia) are as follows.

[0036]

[Chemical 13]

The group represented by RED in formula (Ib) will be described below. RED is a group which is cleaved from A or TIME to become RED-DI and which can be cross-oxidized by an oxidizing substance (for example, an oxidized product of a developing agent) present during development. RED-DI may be any as long as it cleaves DI when oxidized. Examples of RED include hydroquinones, catechols, pyrogallols, 1,4
-Naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamide phenols, hydrazides or sulfonamide naphthols. These groups are specifically described in, for example, JP-A-61-230135,
62-251746, 61-278852, U.S. Pat. Nos. 3,364,022, 3,379,529 and 4,
No. 618571, No. 3639417, No. 468460
4 or J. Org. Chem., 29, 588 (196).
4) are mentioned. Among the above, preferable RED is hydroquinone, 1,4-naphthohydroquinone, 2 (or 4) -sulfonamidophenol, pyrogallol or hydrazide. Among these, the redox group having a phenolic hydroxyl group is bonded to A at the oxygen atom of the phenol group.

The compound represented by the general formula (Ia) or (Ib) was added until the silver halide photographic light-sensitive material containing the compound represented by the general formula (Ia) or (Ib) was developed. For the purpose of fixing to the photosensitive layer or the non-photosensitive layer, the compound represented by the general formula (Ia) or (Ib) preferably has a diffusion resistant group, and the diffusion resistant group is TIM.
Particularly preferred is when it is contained in E or RED. In this case, the preferred diffusion resistant group is an alkyl group having 8 to 32 carbon atoms, preferably 10 to 20 carbon atoms and an alkyl group (having 3 carbon atoms).
To 20), an alkoxy group (having 3 to 20 carbon atoms), or an aryl group having at least one aryl group (having 6 to 20 carbon atoms).

Regarding the method for synthesizing the compound represented by the general formula (Ia) or (Ib), known patents or references cited for explaining TIME, RED and DI, JP-A-61-156127 and JP-A-61-156127. -160954,
58-162949, 61-249052, 63-37350, US Pat. No. 5,026,628,
It is shown in European Patent Publication No. 443530A2.

Specific representative examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

The precursor releasing compound of the development inhibitor represented by the above general formula (I) of the present invention can be used in any layer in the light-sensitive material. That is, a photosensitive layer (a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a blue-sensitive emulsion layer, a donor layer having a multilayer effect having a spectral sensitivity distribution different from those of the main photosensitive layer),
Non-photosensitive layer (for example, protective layer, yellow filter layer,
It can be used for any of the intermediate layer and the antihalation layer). When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any of the highest-sensitivity layer, the lowest-sensitivity layer and the intermediate-sensitivity layer, and to all layers. It can also be added. It is preferably used in the photosensitive layer and / or the non-photosensitive layer adjacent to the photosensitive layer.

The amount of the precursor releasing compound of the development inhibitor represented by the general formula (I) used in the light-sensitive material is 5 × 10 ^-4 to 2
The coating amount is in the range of g / m ² . Preferably 1 × 10 ^-3
To 1 g / m ² , more preferably 5 × 10 ⁻³
The range is from 5 × 10 ⁻¹ g / m ² . Regarding the use of the precursor releasing compound of the development inhibitor represented by the general formula (I) in the light-sensitive material, any known dispersion method can be used depending on the compound. For example, when it is alkali-soluble, it may be added as an alkaline aqueous solution or as a solution dissolved in an organic solvent miscible with water, an oil-in-water dispersion method using a high-boiling organic solvent, or a solid dispersion method. You can

The precursor releasing compound of the development inhibitor represented by the general formula (I) may be used alone or in combination of two or more kinds. Also, the same compound can be used in two or more layers. Furthermore, it can be used in combination with other known development inhibitor releasing compounds and development inhibitor precursor releasing compounds, or can be used in coexistence with couplers and other additives described below. These are appropriately selected according to the performance required of the light-sensitive material.

The precursor-releasing compound of the development inhibitor represented by the general formula (I) of the present invention releases a precursor of the development inhibitor through a coupling reaction with an oxidant of the developing agent and at the same time as its mother nucleus (the above-mentioned). A) in the description of general formula (I) forms a dye. The formed dye is, for example, Volume 52 (1989), No. 2, pages 150 to 155 (Kida e
t al) or 1989 Annual Meeting of the Photographic Society of Japan 2
As described in A0-22 (Kida), it flows out into the processing solution during the color development processing or the dye is bleached and erased. Therefore, the formed dye does not remain on the photosensitive material as a dye after color development processing. Therefore, the precursor-releasing compound of the development inhibitor represented by the general formula (I) of the present invention can be used in any layer constituting the light-sensitive material, such as a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer. There is an advantage that the compound can be used depending on the performance required for the light-sensitive material. Furthermore, since the formed dye does not remain as a dye, it has an advantageous effect on color reproducibility. Further, the color image fastness may be improved in some cases.

The precursor-releasing compound of the development inhibitor represented by the general formula (I) of the present invention is further used in a light-sensitive material together with an oil-soluble dye represented by the general formula (A) described below to further improve color reproducibility and color reproducibility. It improves the image quality such as sharpness and gives excellent storability of photosensitive materials. It also improves photographic sensitivity and color image fastness.

Next, the oil-soluble dye represented by formula (A) used in the present invention will be described in detail. The electron-withdrawing group represented by X and Y has a Hammett σ _p value of 0.
Examples of the above include a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, normal butoxycarbonyl), an aryloxycarbonyl (eg, phenoxycarbonyl, 4-methoxyphenoxycarbonyl), a nitro group. An acyl group (eg, acetyl, pivaloyl, benzoyl, 4-methoxybenzoyl, 4-methanesulfonamidobenzoyl, propionyl, 4-methoxy-3-methanesulfonamidobenzoyl, 1-methylcyclopropylcarbonyl, 1-ethylcyclopropylcarbonyl) A carbamoyl group [eg, N-ethylcarbamoyl, N, N-dimethylcarbamoyl, morpholin-4-ylcarbonyl, N- (3-methanesulfonamidophenyl) carboxyl. Bamoiru], a sulfonyl group (e.g., benzenesulfonyl, p- toluenesulfonyl), a carboxy group, a sulfamoyl group (e.g. sulfamoyl,
N, N-dimethylsulfamoyl group).

The 5-membered ring formed by X and Y is 2-pyrazolin-5-one [eg 3-ethoxycarbonyl-1-
(4-acetylsulfamoyl) phenylpyrazolone,
3-ethoxycarbonyl-1- (4-propionylsulfamoyl) phenylpyrazolone, 3-methyl-1-
(4-benzenesulfonamide) phenylpyrazolone,
3- (4-methanesulfonamido) phenyl-1-methylpyrazolone, 3-ethoxycarbonyl-1- (sulfolan-3-yl) pyrazolone, 3-methyl-1- (4-
Hydroxy-6-methylpyrimidin-2-yl) pyrazolone], 2-isoxazolin-5-one (for example, 3-
tert-Butylisoxazolone, 3-methylisoxazolone, 3- (4-methoxy) phenylisoxazolone, 3- (4-benzenesulfonamido) phenylisoxazolone, 3- (4-toluenesulfonamido) phenylisoxazolone, 3 -(4-methoxy-
3-benzenesulfonamide) phenylisoxazolone, 3- {4- [3,5-bis (methoxycarbonyl))
Benzenesulfonamide]} phenylisoxazolone, 3- {4- (1-ethoxycarbonylpropanesulfonamide)} phenylisoxazolone, 3- (3-
p-toluenesulfonamide) phenylisoxazolone), α, β-unsaturated butenolide (eg 3-cyano-
4- (4-butanesulfonamido) phenyl-2,4-
Dihydro-2 (4H) furanone), β, γ-unsaturated butenolide (eg 4-phenyl-2,3-dihydro-2)
(3H) Furanone), oxazolin-5-one (for example, 2- (4-butanesulfonamido) phenyloxazolone, 2- (4-methanesulfonamido) phenyloxazolone), 5-imidazolone (for example, 1-ethyl-2-).
(4-Methanesulfonamide) phenylimidazolone), indandione (for example, indandione, 5-benzenesulfonamideindanedione, 4-methanesulfonamideindanedione), pyrazolidine-3,5-
Diones (for example, 1,2-bis (4-acetylsulfamoyl) phenylpyrazolidine-3,5-dione) and the like.

The 6-membered ring formed by X and Y is a barbituric acid (eg, N, N'-diethylbarbituric acid, N-ethyl-N '-(4-methanesulfonamide) phenylbarbituric acid, N- Methyl-N '-(4-methanesulfonylcarbamoyl) phenyl barbituric acid, N-methyl-N'-(4-carboxy) phenyl barbituric acid), thiobarbituric acid (eg N, N'-diethylthiobarbituric acid) Acid), 1,2-dihydro-6-hydroxypyridin-2-one (eg 3-cyano-1- (4
-Benzenesulfonamido) phenyl-4-methyl-6
-Hydroxypyridone, 3-carbamoyl-4-methyl-6-hydroxypyridone, 3-carbamoyl-1-
(4-Acetylsulfamoyl) phenyl-4-methyl-6-hydroxypyridone), 3,4,5,7-tetrahydropyrazolo [3,4-b] pyridine) -3,6-dione (eg 2- (4-acetylsulfamoyl) phenyl-4-methylpyrazolopyridinedione) and the like.

The 5-membered heterocyclic ring represented by Ar is indole [eg 1- (2-ethoxycarbonylethyl) indole, 1- (2-methoxyethoxycarbonylethyl)].
Indole, 1- (2-acetoxyethoxycarbonylethyl) indole, 1-cyanoethylindole, 2
-Methyl-1-cyanoethylindole, 5- {3,5
-Bis (methoxycarbonyl) benzenesulfonamide} -1-methoxycarbonylmethylindole, 1-
(2-p-toluenesulfonylcarbamoyl) ethylindole], furan-2-yl or furan-3-yl, thiophen-2-yl, thiophen-3-yl and the like. The 6-membered heterocyclic ring represented by Ar is coumarin (for example, 7-diethylaminocoumarin-3-yl), pyridin-4-yl, pyridin-5-yl and the like.

The methine group represented by L ¹ , L ² and L ³ is a substituent [eg methyl, ethyl or cyano. When n is 2 or 3, it may have a bridge on the methine chain (eg, neopentylidene, propylidene)], but an unsubstituted methine group is preferable.

However, the chromophore of the dye represented by the above-mentioned general formula (A) does not have a carboxyl ion type chromophore.

The dye represented by the general formula (A) of the present invention is an oil-soluble dye. The term "oil-soluble" as used in the present invention means a dye which is water-insoluble and has a solubility of 0.1 g or less per liter of distilled water at 25 ° C.

In the present invention, the dye represented by the general formula (A) is preferably represented by the general formula (A
It is a dye represented by -1).

[0064]

[Chemical formula 24]

In the formula, R ²¹ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a ureido group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkylthio group, an arylthio group, an oxycarbonyl group, It represents an acyl group, a carbamoyl group, a cyano group, an alkoxy group, an aryloxy group, an amino group, or an amide group. Q is -O- or -NR ²² - represents, R
²² represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ²³ , R ²⁴ and R ²⁵ are each independently a hydrogen atom,
It represents an alkyl group or an aryl group, and includes forming a 6-membered ring with R ²⁴ and R ²⁵ . R ²⁶ is a hydrogen atom, an alkyl group,
It represents an aryl group or an amino group. k is 0 or 1
Is. However, when Q is —NR ²² —, R ²⁴ and R ²⁵ form a 6-membered condensed ring.

The dye represented by formula (A-1) will be described in detail below. The alkyl group represented by R ²¹ may have a substituent, and is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, tert-butyl,
Normal butyl, 1-methylcyclopropyl, chloromethyl, trifluoromethyl, ethoxycarbonylmethyl and the like are preferable.

The aryl group represented by R ²¹ may have a substituent and is preferably an aryl group having 6 to 13 carbon atoms, for example, phenyl, 4-methoxyphenyl, 4-acetylaminophenyl and 4-methane. Sulfonamidophenyl and 4-benzenesulfonamidophenyl are preferred.

The alkyl group represented by R ²² may have a substituent and is preferably an alkyl group having 1 to 18 carbon atoms, such as methyl, 2-cyanoethyl, 2-hydroxyethyl and 2-acetoxyethyl. preferable.

The phenyl group or substituted phenyl group represented by R ²² is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 3,5-di (ethoxycarbonyl) phenyl,
4-di (ethoxycarbonylmethyl) aminocarbonylphenyl, 4-normaloctyloxycarbonylphenyl, 4-butanesulfonamidocarbonylphenyl,
4-methanesulfonamidocarbonylphenyl, 3-sulfamoylphenyl, 4-methanesulfonamidophenyl, 4-methanesulfonamidosulfonylphenyl,
4-Acetylsulfamoylphenyl, 4-propionylsulfamoylphenyl, 4-N-ethylcarbamoylsulfamoylphenyl and the like are preferable.

The heterocyclic group represented by R ²² is pyridyl, 4-hydroxy-6-methylpyrimidin-2-yl, 4-hydroxy-6-tert-butylpyrimidin-2-.
And sulfolan-3-yl.

The alkyl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl or propyl. A methyl group is particularly preferable.

The aryl group represented by R ²³ , R ²⁴ and R ²⁵ is preferably an aryl group having 6 to 13 carbon atoms, and particularly preferably a phenyl group. The 6-membered ring formed by R ²⁴ and R ²⁵ may be saturated, unsaturated or a heterocyclic ring, but a benzene ring is particularly preferable.

The alkyl group represented by R ²⁶ may have a substituent, and is preferably an alkyl group having 1 to 18 carbon atoms,
For example, methyl, ethyl, ethoxycarbonylmethyl, tert-butoxycarbonylmethyl, ethoxycarbonylethyl, dimethylaminomethyl, 2-cyanoethyl, 3-acetamidopropyl, 3-propionylaminopropyl, 3-benzenesulfonamidopropyl, 3-propanesulfonamide. Propyl and the like are preferred.

The phenyl group or substituted phenyl group represented by R ²⁶ is preferably a phenyl group having 6 to 22 carbon atoms, for example, phenyl, 2-methoxy-5-ethoxycarbonylphenyl, 4-di (ethoxycarbonylmethyl) aminocarbonylphenyl. , 4-normaloctyloxycarbonylphenyl, 4-hydroxyethoxycarbonylphenyl, 4-propanesulfonamidophenyl, 4-butanesulfonamidocarbonylphenyl, 4-methanesulfonamidosulfonylphenyl, 4-acetylsulfamoylphenyl are preferred.

The amino group represented by R ²⁶ is preferably a dialkylamino group, for example, dimethylamino and diethylamino.

The compound represented by formula (A-1) preferably does not contain a sulfo group, a salt of a sulfo group, a carboxy group or a salt of a carboxy group as a substituent.

The compound represented by formula (A-1) preferably has a dissociative group other than the above. Examples of preferred dissociative properties include substituted sulfonylamino groups (eg CH
_{3 SO 2 NH-, C 6 H} 5 SO 2 NH -), acyl sulfamoyl group,
There are a sulfonylsulfamoyl group, a sulfonylcarbamoyl group, and a carbamoylsulfamoyl group.

Specific examples of the compound represented by formula (A) are shown below, but the invention is not limited thereto.

[0079]

[Chemical 25]

[0080]

[Chemical formula 26]

[0081]

[Chemical 27]

[0082]

[Chemical 28]

[0083]

[Chemical 29]

The dye represented by formula (A) of the present invention can be used in any of the layers constituting the light-sensitive material. It is preferably a non-photosensitive layer, and particularly preferably used for a non-photosensitive layer adjacent to the side of the blue-sensitive photosensitive layer closer to the support. The addition amount of the dye represented by formula (A) of the present invention is 2 × 10 ^{−5 to} 5 × 10 ⁻³ mol / m 2.
^{Is 2} . Preferably 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / m
It is in the range of ² . Two or more kinds of dyes can be used in combination, and if necessary, two or more layers can be used.
In order to introduce the dye represented by the above general formula (A) of the present invention into the light-sensitive material, a method of adding a dispersion dispersed using a known dispersion method can be applied. For example, a method of dissolving in a high-boiling organic solvent and / or a low-boiling organic solvent and finely dispersing it in a hydrophilic colloid medium such as gelatin,
A latex dispersion method, a dispersion method using a polymer, a solid dispersion method or the like can be applied. In particular, it is preferable to apply the oil-in-water dispersion method using a high boiling point organic solvent. When a dispersion is prepared by applying these dispersion methods, it may be a dispersion of the dye of the present invention alone or a dispersion in which other known dyes are mixed. Further, other known additives such as antifoggants, stabilizers, color mixing inhibitors, stain inhibitors, ultraviolet absorbers, chemical sensitizers, sensitivity enhancers, and sensitizers are added depending on the performance required of the light-sensitive material. It may be a dispersion in which a white agent, a dye image stabilizer and the like are mixed.

In the present invention, the gelatin coating amount of the layer containing the dye represented by formula (A) of the present invention is 1.5 g / m ² or less. Preferably 1.2 g / m
² or less and 0.2 g / m ² or more, and more preferably 1.
It is 0 g / m ² or less and 0.3 g / m ² or more. When the gelatin coating amount exceeds 1.5 g / m ² , the dye elutes from the light-sensitive material or decolorizes (bleachs) during the color development process.
Will be delayed, resulting in deterioration of image quality due to residual color. Not only that, the development of the photosensitive silver halide emulsion layer coated on the side closer to the support than the layer containing the dye is delayed in color development, or remains after processing due to delay in desilvering process. This is not preferable because the amount of silver increases and the photographic properties and image quality deteriorate.

The dye represented by the general formula (A) of the present invention is effective for improving the image quality, particularly the color reproducibility. However, the precursor release agent for the development inhibitor represented by the general formula (I) of the present invention is released. When used in combination with the compound, the color reproducibility can be further improved by improving the desilvering property, and the excellent effect of improving the storability of the light-sensitive material with time and the fastness of the color image can be brought about.

Next, the compound represented by formula (II) will be described in detail. R ₁ is -CONR ₄ R ₅ , -S
_{O 2 NR 4 R 5, -NHCOR} 4, -NHCOOR 6,
_{-NHSO 2 R 6, -NHCONR 4 R} 5 or -NHS
Represents O ₂ NR ₄ R ₅ , and R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 30 C atoms, or a C number 2; ~ 3
Represents a heterocyclic group of 0. R ₄ and R ₅ may also be hydrogen atoms.

R ₂ represents a group capable of substituting on a naphthalene ring (including atoms; the same applies hereinafter), and representative examples thereof include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbonyl group, an amino group and a sulfo group. , Cyano group, alkyl group, aryl group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Examples thereof include an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group and an imide group. Examples of when k = 2 include a dioxymethylene group and a trimethylene group.
The C number of (R ₂ ) _k is 0 to 30.

R ₃ represents a substituent, preferably represented by the following formula (II-1). Formula (II-1) R ₇ (Y) _m − In formula (II-1), Y is>NH,> CO or> SO.
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, a C 1-30 alkyl group, a C 6-30 aryl group, C
A heterocyclic group of the number 2 to 30, -COR ₈ ,

[0090]

[Chemical 30]

Or —SO ₂ R ₁₀ respectively. Here, R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively. In R ₁ or R ₇ , -N
R _{4 and} R ₅ of R ₄ R ₅ and R ₈ and R ₉ of —NR ₈ R ₉ may be bonded to each other to form a nitrogen-containing heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring).

X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (referred to as a splitting group. The splitting atom is included. The same applies hereinafter), and a typical example of the splitting group. As a halogen atom,

[0093]

[Chemical 31]

A thiocyanate group and a heterocyclic group having a C number of 1 to 30 and bonded to a coupling active position at a nitrogen atom (eg, succinimide group, phthalimido group, pyrazolyl group, hydantoinyl group, 2-benzotriazolyl group) are used. Can be mentioned. Here, R ₁₁ has the same meaning as R ₆ .

In the above, the alkyl group may be linear, branched or cyclic, and may have a substituent (eg halogen atom, hydroxyl group, aryl group, heterocyclic group) even if it contains an unsaturated bond. , An alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and representative examples include methyl, isopropyl, isobutyl, t-butyl, 2- Ethylhexyl, cyclohexyl, n-dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-
There is t-pentylphenoxy) propyl.

Even if the aryl group is a condensed ring (for example, naphthyl group), a substituent (for example, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group), phenyl as a representative example,
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

The heterocyclic group is O, N, S, P, Se or T.
a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one hetero atom of e in the ring, which is a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), As typical examples, 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
There are 1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

Examples of preferable substituents in the present invention will be described below. R ₁ is -CONR ₄ R ₅ or -SO
₂ NR ₄ R ₅ is preferable, and specific examples include carbamoyl,
N-n-butylcarbamoyl, Nn-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3
-(2,4-di-t-pentylphenoxy) propyl]
Carbamoyl, N-hexadecylcarbamoyl, N-
[4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methylpropyl) carbamoyl, N- [3- (4-t-octylphenoxy) propyl] carbamoyl , N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,
4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ is particularly preferably -CONR ₄ R ₅ .

As R ₂ and k, k = 0, that is, unsubstituted one is most preferable, and then k = 1. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl,
It is isopropyl, t-butyl, cyclopentyl), a carbonamide group (eg acetamide, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (eg methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m in formula (II-1).
= 0, more preferably R ₇ is —COR ₈ [eg formyl, acetyl, trifluoroacetyl, 2-
Ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentylphenoxy) butanoyl], -COOR ₁₀ [eg methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-
Dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or —SO ₂ R ₁₀ [eg methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-
Chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably R ₇ is —COOR ₁₀ .

X is preferably a hydrogen atom, a halogen atom,
-OR ₁₁ [eg ethoxy, 2-hydroxyethoxy,
2-methoxyethoxy, 2- (2-hydroxyethoxy) ethoxy, 2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy. Two
An alkoxy group such as methanesulfonamidoethoxy, 2- (carboxymethylthio) ethoxy, 2- (1-carboxytridecylthio) ethoxy; eg 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t -Octylphenoxy, 4-nitrophenoxy, 4- (3-carboxypropanamide)
Phenoxy, an aryloxy group such as 4-acetamidophenoxy], or -SR ₁₁ [for example, carboxymethylthio, 2-carboxyethylthio, 2-methoxyethylthio, ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2- ( Alkylthio groups such as N, N-dimethylamino) ethylthio; eg 4-carboxyphenylthio, 4-methoxyphenylthio, 4
An arylthio group such as-(3-carboxypropanamide) phenylthio], and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula (II) may form a bis form in the substituents R ₁ , R ₂ , R ₃ or X, and they are bonded to each other through a divalent or divalent or higher valent group. Dimers or higher multimers may be formed. In this case, the carbon number range shown in each of the above substituents may be out of the range. When the coupler represented by the general formula (II) forms a multimer, a typical example is a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue, It is preferably represented by formula (II-2). Formula (II-2) - (G i) gi - (H j) hj - group represented by the formula G _i is a repeating unit derived from the color forming monomer formula (II-2) (II- 3) H _j is a repeating unit derived from a non-color-forming monomer, i is a positive integer, j is 0 or a positive integer, and gi and hi are the weight fractions of G _I or H _j , respectively. Represents Here, when i or j is plural, G _i or H _j means containing plural kinds of repeating units. Formula (II-3)

[0103]

[Chemical 32]

In the formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A
Represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms below both such as a substituted or unsubstituted alkylene group, a phenylene group or an oxydialkylene group. And L is-
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - SO 2 -, - NHSO
₂ -, or represents a -SO ₂ NH-. a, b, c are 0
Or represents an integer of 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ , R ₃ or X of the compound represented by the general formula (II).

Examples of the non-color-forming, ethylene-type monomer that does not couple with the oxidation product of the aromatic primary amine developing agent which gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid and α-alkylacrylic acid. (Eg, methacrylic acid, etc.), amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate). , N-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl meta. Rilates and β-hydroxyethylmethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, eg vinyltoluene, divinylbenzene, vinyl). Acetophenone and sulfostyrene), itaconic acid, citraconic acid,
Examples include crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type 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 well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above formula (II-3) is in the form of the copolymer to be formed, for example, solid. , Liquid, micelles and physical and / or chemical substances such as solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized product of a developing agent, and diffusion resistance in a photographic colloid can be favorably influenced. These copolymers may be random copolymers or copolymers having a specific sequence (for example, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of several thousands to several millions, but oligomeric polymer couplers of 5000 or less can also be used. The cyan polymer coupler used in the present invention is an organic solvent (for example, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone,
Whether it is a lipophilic polymer soluble in dibutyl phthalate or tricresyl phosphate) or a hydrophilic polymer miscible with a hydrocolloid such as an aqueous gelatin solution, it has a structure and properties capable of forming micelles in the hydrocolloid. It may be a polymer having.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color-forming ethylenic monomer (eg acrylic acid ester, methacrylic acid ester, maleic acid ester, vinylbenzenes, etc.) is mainly used as a copolymerization component. Is preferred. The general formula (II-
It may be prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by 3) in an organic solvent and emulsifying and dispersing it in an aqueous gelatin solution in the form of latex. It may be prepared by an emulsion polymerization method.

A method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,311. 370,952
The method described in the publication can be used. Alternatively, in order to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-sulfonateethyl) acrylamide, 3-sulfonatepropylacrylate, sodium styrenesulfonate, Styrene potassium sulfinate, acrylamide,
It is preferable to use a hydrophilic non-color forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. as the copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and an organic solvent miscible with water such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide and dimethylacetamide. It can also be dissolved in a mixed solvent of water and water and added. Furthermore, it may be added after being dissolved in an alkaline aqueous solution or an organic solvent containing alkaline water. Also, a small amount of surfactant may be added.

Specific examples of each substituent in the formula (II) and the cyan coupler represented by the formula (II) are shown below.

Examples of R ₁

[0114]

[Chemical 33]

[0115]

[Chemical 34]

[0116]

[Chemical 35]

[0117]

[Chemical 36]

Examples of R ₂

[0119]

[Chemical 37]

Examples of R ₃ NH-

[0121]

[Chemical 38]

[0122]

[Chemical Formula 39]

[0123]

[Chemical 40]

[0124]

[Chemical 41]

[0125]

[Chemical 42]

Example of X

[0127]

[Chemical 43]

[0128]

[Chemical 44]

[0129]

[Chemical formula 45]

[0130]

[Chemical formula 46]

Specific examples of the cyan coupler represented by the general formula (II)

[0132]

[Chemical 47]

[0133]

[Chemical 48]

[0134]

[Chemical 49]

[0135]

[Chemical 50]

[0136]

[Chemical 51]

[0137]

[Chemical 52]

[0138]

[Chemical 53]

[0139]

[Chemical 54]

Specific examples of the cyan coupler represented by the formula (II) other than the above and / or a method for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, JP-A-60.
-237448, 61-153640, 61-
No. 145557, No. 63-208042, No. 64-3
1159 and West German Patent No. 3823049A. The cyan coupler represented by the formula (II) is
As described in JP-A-62-269958,
It is preferable to use a small amount of a high boiling point organic solvent for dispersion in order to further improve the sharpness and desilvering property.

Specifically, the high boiling point organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less, relative to the cyan coupler represented by the formula (II). The cyan coupler represented by the formula (II) is preferably used in combination of two or more kinds. When the same color sensitivity is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is used in the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use either or both of the same color-sensitive layers other than those.

Next, the phenol cyan coupler represented by formula (III) will be described in detail below. In the general formula (III), R ¹ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 (preferably 4 to 30) total carbon atoms (hereinafter referred to as C number),
An optionally substituted aryl group having a C number of 6 to 36 (preferably 12 to 30) or a C number of 2 to 36 (preferably 1)
2 to 30) is represented. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring, and examples As 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl,
There are 2-imidazolyl, 4-quinolyl and the like. Examples of the substituent of R ¹ include a halogen atom, a cyano group, a nitro group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino Group, ureido group, alkoxylcarbonylamino group or sulfamoylamino group (hereinafter referred to as substituent group A),
Examples of preferable substituents are an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In the general formula (III), R ² has a C number of 6 to 36.
It represents an aryl group (preferably 6 to 15) and may be substituted with a substituent selected from the above-mentioned Substituent group A or may be a condensed ring. Here, as a preferable substituent, a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), alkoxy groups (eg methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p). -Chlorophenylsulfonyl), an alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Bamoiru group (e.g. N, N- dimethylcarbamoyl, N- phenylcarbamoyl), or a sulfamoyl group (e.g. N, N
-Diethylsulfamoyl, N-phenylsulfamoyl). R ² is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Trifluoromethylphenyl or 3-sulfon A Dofeniru, particularly preferably 4-cyanophenyl, 3-cyano -
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (III), Z represents a hydrogen atom or a coupling-off group which can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Examples of coupling-off groups include halogen atoms, sulfo groups,
An alkoxy group having a C number of 1 to 36 (preferably 1 to 24),
An aryloxy group having a C number of 6 to 36 (preferably 6 to 24), an acyloxy group having a C number of 2 to 36 (preferably 2 to 24), an alkylsulfonyl group having a C number of 1 to 36 (preferably 1 to 24), Arylsulfonyl group having a C number of 6 to 36 (preferably 6 to 24), C number of 1 to 36 (preferably 2 to)
24) alkylthio group, C number of 6 to 36 (preferably 6)
To 24) arylthio group, C number of 4 to 36 (preferably 4 to 24) imide group, C number of 1 to 36 (preferably 1 to 36)
24) a carbamoyloxy group or a heterocyclic group bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24) (eg pyrazolyl, imidazolyl,
1,2,4-triazol-1-yl, tetrazolyl)
There is. Here, the following groups are the alkoxy groups A
It may be substituted with a substituent selected from Z is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group thio group, and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an aryloxy group.

Specific examples of R ¹ , R ² and Z in the general formula (III) are shown below.

Examples of R ¹

[0147]

[Chemical 55]

[0148]

[Chemical 56]

[0149]

[Chemical 57]

[0150]

[Chemical 58]

[0151]

[Chemical 59]

[0152]

[Chemical 60]

[0153]

[Chemical formula 61]

Examples of R ²

[0155]

[Chemical formula 62]

[0156]

[Chemical formula 63]

Example of Z

[0158]

[Chemical 64]

[0159]

[Chemical 65]

[0160]

[Chemical formula 66]

[0161]

[Chemical formula 67]

Specific examples of the cyan coupler represented by the general formula (III) are shown below. However, A to Z and a to f are
5, 56, 57, 58, 59, 60, 61
It is a serial number of a specific example of R ¹ in.

[0163]

[Table 1]

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

[Table 4]

[0167]

[Table 5]

The cyan coupler represented by the general formula (III) is described in, for example, JP-A-56-65134 and 61-2757.
No. 63-159848, No. 63-161450.
No. 63-161451, JP-A No. 1-254956.
And US Pat. No. 4,923,791. In the present invention, when the cyan couplers represented by the general formula (II) and the general formula (III) are used in combination, the use ratio of the coupler of the general formula (II) and the coupler of the general formula (III) can be arbitrarily set. That is, the general formula (II): general formula (III) is 99.9: 0.1
It can be taken in a ratio of 0.1: 99.9 (molar ratio). In the present invention, the total amount of the cyan couplers represented by the general formulas (II) and (III) is 1 × 10 ⁻³ to 2 mol per mol of silver halide when used in the photosensitive layer. It is a range. It is preferably in the range of 1 × 10 ^-2 to 1 mol,
More preferably, it is in the range of 2 × 10 ^{-2 to} 0.5 mol.
When used in the non-photosensitive layer, it is in the range of 1 × 10 ⁻³ to 1 mol per mol of silver halide in the adjacent photosensitive layer. The amount is preferably 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 5 × 10 ⁻³ to 2 × 10 ⁻¹ mol.

The cyan couplers represented by the general formulas (II) and (III) of the present invention can be introduced into the light-sensitive material by any known dispersion method, but preferably the oil-in-water described below is used. This is a method of adding a dispersion using a drop dispersion method.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion 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 on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. 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 the green color. 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 photosensitive 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. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
13438, 59-113440, 61-20037, 61-20038
It may contain a coupler, a DIR compound or the like as described in JP-A No. 1994-242, and may contain a color mixing inhibitor as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of two layers, 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. Can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-11275
No. 1, 62-200350, 62-206541, 62-206543
As described in the publications, 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 (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH
/ BL / GL / GH / RH / RL in order or BH / BL / GH / GL / RL
/ RH can be installed in that order. In addition, Japanese Examined Sho 55-349
As described in Japanese Patent No. 32,32, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest photosensitivity,
The middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than the middle layer. The photosensitivity is gradually reduced toward the support. An arrangement composed of three layers 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 layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order. In addition, they 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 or more layers, the arrangement may be changed as described above. U.S. Pat.Nos. 4,663,271 and 4,705,744 to improve color reproduction
No. 4,707,436, JP-A-62-160448, 63-89850
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL, which is described in the above publication, 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 light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains 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 production (Emulsi
on preparation and types) ”, and No. 18716 (1979)
No. 307105 (November 1989), 863-865, p. 648, p. 648.
Page, and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chimie et Physique Photo
graphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Phot
ographic Emulsion Chemistry (Focal Press, 1966)),
Zelikman et al., "Manufacturing and Coating of Photographic Emulsions", published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have different halogen compositions in the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to 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 emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. 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. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more 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,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used in the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus 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 whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. 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 ± 40% of the average grain size). %) Is preferable).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it 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. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. 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 this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 5.fogging prevention page 24-25 page 649 right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizer, page 27 650 pages right column 876 lubricants 12. Coating aids , Pages 26-27, page 650, right column, pages 875-876, surface active agent, 13. static, page 27, page 650, right column, pages 876-877, inhibitors, matting agents, pages 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-2835
It is preferable to contain the mercapto compound described in No. 51. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, in addition to the dye represented by the general formula (1), international publication WO88 / 04794 and Japanese Patent Publication No. 1-502912.
Dyes or European Patent No.
317,308A, U.S. Pat.No. 4,420,555, JP-A 1-259358
It is preferable to include the dyes described in No. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, mentioned above.
VII-C to G, and the patents described in No. 307105 and VII-C to G. As the yellow coupler, for example, U.S. Patent Nos. 3,933,501 and 4,022,620,
4,326,024, 4,401,752, 4,248,961, JP 58-10739, British Patent 1,425,020, 1,47
6,760, U.S. Pat.Nos. 3,973,968, 4,314,023,
Those described in U.S. Pat. No. 4,511,649 and European Patent No. 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,636 are preferred.
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), Japanese Patent Laid-Open No. 60-33552, Research Disclosure No. 24230.
(June 1984), JP-A-60-43659, 61-72238,
60-35730, 55-118034, 60-185951, U.S. Pat.Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 are particularly preferable.
As the cyan coupler, the general formula (II) and the general formula (I
In addition to the couplers described in II), U.S. Pat.
No. 12, No. 4,146,396, No. 4,228,233, No. 4,296,200
No. 2,369,929, 2,801,171, 2,772,162
Issue 2, Issue 2,895,826, Issue 3,772,002, Issue 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No.
3,329,729, European Patents 121,365A, 249,453A,
U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,6
No. 16, No. 4,451,559, No. 4,427,767, No. 4,690,889
No. 4,254,212, 4,296,199, JP-A-61-42658
The couplers described in No. etc. can also be used in combination. Further, JP-A 64-553, 64-554, 64-555, 64-5
The pyrazoloazole-based couplers described in 56 and the imidazole-based couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,211.
No. 4,367,282, 4,409,320, 4,576,910
No. 2,102,137, European Patent No. 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 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication) 3,
Those described in No. 234,533 are preferable. Colored couplers to correct unwanted absorption of colored dyes are
Disclosure No.17643, Item VII-G, No.30710
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
Those described in 9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. Also,
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in U.S. Pat.No. 4,774,181, and a dye precursor group capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases a development inhibitor includes, in addition to the compound represented by the general formula (I), RD No. 17643, Item VII-F and N.
Patents described in o.307105, VII-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248, No. 63-37346
No. 63-37350, U.S. Pat.Nos. 4,248,962, 4,782,
Those described in No. 012 can be used. RD N
The bleaching accelerator releasing couplers described in JP-A No. 11449, No. 24241, JP-A-61-201247 and the like are effective for shortening the time of the processing step having a bleaching ability, and in particular, the above-mentioned tabular form. The effect is great when it is added to a light-sensitive material using silver halide grains. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,0
97,140, 2,131,188, JP-A-59-157638, 59
Those described in -170840 are preferable. In addition, JP 60-1
07029, 60-252340, JP-A-1-44940, 1-45
Compounds releasing a fogging 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 687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in No. 8,393 and No. 4,310,618,
DI described in JP-A-60-185950 and JP-A-62-24252
R redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No.
Nos. 173,302A and 313,308A, couplers that release dyes that recolor after separation, ligand-releasing couplers described in U.S. Pat. Examples thereof include couplers and couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling 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, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, 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,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (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 include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. 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, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. 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 55% relative humidity (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 (Photogr. S) by A. Green et al.
ci. & Eng.), 19 Certificates, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 90% of the maximum swollen film thickness reached after processing for 15 minutes is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (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-
500% is preferable.

The color photographic light-sensitive material according to the present invention is described in RD No. 17643, pages 28 to 29, RD No. 18716, 651 left column to right column, and No. 307105, page 880 to 881. Development can be carried out by a conventional method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline.
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino
-N-ethyl-β-methoxyethylaniline, 4-amino-3
-Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl -N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl
-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or Sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose. Color developers include alkaline metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, 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 Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone 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 replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 m 2 of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented 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, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit developing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. 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 color developing agent at a high concentration.

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 can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Of these, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts 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 bleach accelerators are described in the following publications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salt described in JP-A-58-16235; West German Patent No. 966,41
No. 0, No. 2,748,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, 49-59644, 53-94927,
Compounds described in Nos. 54-35727, 55-26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. 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. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. 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, but the use of thiosulfates is common. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. 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 294,769A 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, a fixing solution or a bleach-fixing solution is used for adjusting the pH.
Compounds having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-
It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is as strong as possible.
As a specific method for strengthening stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means of JP-A-62-183461 are used. Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with a wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the 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 consequently 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 action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. JP-A-60 mentioned above
As described in No. 191257, such a transportation 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 deterioration of the performance 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 subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, 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 water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Volume 64, pp. 248-253 (May 1955)
It can be obtained by the method described in (Month issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method for reducing calcium ion and magnesium ion described in No. 62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used. In the processing of the light-sensitive material of the present invention, the washing water has a pH of 4 to
9, and preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used. Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. 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 also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the supplement 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, indaniline-based compounds described in U.S. Pat. Metal salt complex described in JP-A-53-13562
The urethane compounds described in No. 8 can be mentioned. The silver halide color light-sensitive material of the present invention, if necessary,
Various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of accelerating color development. Typical compounds are
56-64339, 57-144547 and 58-115438. Various treatment liquids in the present invention are 10 ℃ ~ 50
Used at ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit effects when applied to a lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0192]

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,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0194]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1.5 × 10 ^-5 ExS-3 4.5 × 10 ^-4 IIC-7 0.17 IIC-34 0.030 III C-2 0.11 ExC-2 0.0050 ExC-4 0.0050 ExC-5 0.020 Cpd-2 0.025 HBS-1 0.10 HBS-4 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 IIC-7 0.15 ExC-1 0.060 III C-2 0.12 ExC-4 0.0010 ExC-5 0.025 Cpd-2 0.023 HBS-1 0.10 HBS-5 0.050 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.0 × 10 ^-4 IIC-7 0.043 IIC-34 0.040 III C-2 0.063 ExC-3 0.020 ExC-5 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion C Silver 0.17 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExS-8 8.0 × 10 ^-4 ExS-10 3.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 Comparative coupler (1) 0.015 HBS-1 0.30 HBS-3 0.010 HBS-5 0.10 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExS-9 7.0 × 10 ^-4 ExS-10 2.5 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 Comparative coupler (1) 0.01 Comparative coupler (2) 0.030 HBS-1 0.10 HBS-3 8.0 × 10 ^-3 HBS-4 0.10 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExS-8 2.5 × 10 ^-4 ExS-9 2.5 × 10 ^-4 Comparative coupler (3) 0.020 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.16 HBS-1 0.15 HBS-5 0.10 Gelatin 0.65

11th layer (low-sensitivity blue emulsion layer) Emulsion C Silver 0.25 Emulsion D Silver 0.40 ExS-7 8.0 × 10 ^-4 ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-4 0.01 HBS-1 0.25 HBS-5 0.10 Gelatin 1.30

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.38 ExS-7 3.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 HBS-4 0.030 Gelatin 0.86

Thirteenth layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

14th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0208]

[Table 6]

In Table 6, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0210]

[Chemical 68]

[0211]

[Chemical 69]

[0212]

[Chemical 70]

[0213]

[Chemical 71]

[0214]

[Chemical 72]

[0215]

[Chemical formula 73]

[0216]

[Chemical 74]

[0217]

[Chemical 75]

[0218]

[Chemical 76]

[0219]

[Chemical 77]

[0220]

[Chemical 78]

[0221]

[Chemical 79]

[0222]

[Chemical 80]

[0223]

[Chemical 81]

[0224]

[Chemical formula 82]

[0225]

[Chemical 83]

[0226]

[Chemical 84]

Subsequently, the following samples were prepared. (Sample 102) The comparative coupler (1) used in the seventh layer of the green-sensitive emulsion layer of Sample 101 was added to the compound (25) represented by the general formula (I) of the present invention, and the comparative coupler (1) used in the eighth layer ( 1) and 2) are converted to compounds (25) and (22) of the present invention.
Then, a sample was prepared by replacing the comparative coupler (3) used in the ninth layer with the compound (30) of the present invention in an equimolar amount. (Samples 103 and 104) Yellow colloidal silver used for the tenth yellow filter layer of Samples 101 and 102 was removed, and instead of colloidal silver, dye D-22 represented by the general formula (A) of the present invention was applied. Is 4.0 × 10 ^-4 mol / m ²
To prepare a sample (at this time, the dye is H
A dispersion was prepared using BS-1 and HBS-5,
The total HBS-1 and HBS-5 coverages of the layers were made the same).

(Samples 105 to 114) Seventh of Sample 104
The compound (25) of the layer, (25) and (22) of the eighth layer, and (30) of the ninth layer are other compounds represented by the general formula (I) of the present invention as shown in Tables 7 to 9. Samples were prepared by substituting each of them with equimolar amounts. (Samples 115 to 118) The dye D-22 represented by the general formula (A) of the present invention used for the tenth yellow filter layer of the sample 104 was equimolar to another dye represented by the same general formula (A). Samples were prepared by replacing the amounts. Coating amount of gelatin 0.65 g / m ^2, respectively 0.50 g / m ² of the yellow filter layer of the 10 layers (Sample 119, 120) Sample 104 was prepared sample was reduced to 0.40 g / m ^2. (Sample 121) A sample was prepared by replacing the dye D-22 represented by the general formula (A) of the present invention used in the tenth yellow filter layer of the sample 104 with the comparative dye (1) in an equimolar amount. The comparative dye is shown in Chemical Formula 85.

[0229]

[Chemical 85]

The samples 101 to 120 thus produced were subjected to the color development processing shown below, and the following performances were examined. (1) Gradation exposure of photographic white light (color temperature of light source: 4800 ° K)
Measure the density of the sample obtained by performing color development processing,
From the characteristic curve of magenta density, the logarithm of the reciprocal of the exposure amount that gives the density of minimum density + 0.2 was obtained, and using this as the sensitivity, the difference (ΔS _G ) was calculated based on the value of Sample 101. (2) Storage stability of photographic material Two sets were prepared for each sample, one set under conditions of 5 ° C and 30% relative humidity, and another set under conditions of 50 ° C and 80% relative temperature. Each was stored for 5 days. After the test was completed, these two sets of samples were subjected to white light gradation exposure, and after color development processing, the sensitivity was determined by the same method as in (1) above, and the samples were stored under the conditions of 5 ° C. and a relative humidity of 30%. The difference (ΔS ₁ ) was obtained based on the value of the sample. (3) Color image fastness After measuring the magenta density of the sample which was subjected to the gradation exposure of white light, the magenta density was measured and then 30
After storing for a day, perform the density measurement again, and read the density after the end of the test at the point of the exposure amount that gives the density of the minimum density before the start of the magenta density test + 1.5, and subtract the minimum density value from this value. Was divided by a density of 1.5 to obtain the percentage, which was taken as the color image residual rate (D%). (4) Color reproducibility (color turbidity) G and B densities of a magenta color image of a color-developed sample were measured by applying gradation exposure with a green separation filter, and the minimum G density +2.0. The B density at the point of the exposure amount giving the density of 1 was obtained, and the value obtained by subtracting the B density value of the minimum density portion was taken as color turbidity and used as one scale for the evaluation of color reproducibility. The smaller the value, the less the color turbidity and the better the color reproducibility.

Color development processing used in this embodiment will be described below. As for the treatment, a sample to which imagewise exposure had been separately applied was continuously treated until the replenisher for color development was replenished by 3 times the tank capacity, and then the treatment of the sample for examining the performance was conducted. The processing steps and the composition of the processing liquid are shown.

(Processing process) Process processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liters Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liters Stable (1) 20 seconds 38.0 ℃ -3 liters Stable (2) 20 seconds 38.0 ℃ 560 ml 3 liters Dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material

The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the rinsing process were each 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Iodine Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water Add 1.0 liter 1.0 liter pH (prepared with ammonia water) 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (P
H7.0)

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (Prepared with ammonia water and acetic acid) 7.4 7.45

(Wash water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH type strongly basic anion exchange resin (the same Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / l or less, followed by sodium diisocyanurate dichloride 20 mg / l and sodium sulfate 1
50 mg / l was added. The pH of this solution is 6.5.
It was in the range of ~ 7.5.

(Stabilizer) Common to tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2 1,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The results are summarized in Tables 7-9.

[0241]

[Table 7]

[0242]

[Table 8]

[0243]

[Table 9]

From the results of Tables 7 to 9, samples 104 to 1 using the precursor releasing compound of the development inhibitor represented by the general formula (I) of the present invention and the dye represented by the general formula (A) were used.
It is apparent that No. 20 has higher photographic sensitivity than Comparative Samples 101 to 103 and 121, and is excellent in aging storage of the light-sensitive material, color image fastness and color reproducibility. Even if the precursor-releasing compound of the development inhibitor represented by the general formula (I) of the present invention is a compound having a mother nucleus of an open chain ketomethylene type yellow coupler or a naphthol type cyan coupler, the yellow absorption density in a magenta color image. Samples 104 to 12 are excellent in color reproducibility with low color turbidity.
It can be seen from the comparison between No. 0 and Samples 101 and 103. By replacing the yellow colloidal silver of the yellow filter layer with the dye represented by the general formula (A) of the present invention, the sensitivity of photographic properties of the green-sensitive emulsion layer is remarkably increased. Sample 10 can be highly sensitive
It can be known from the comparison between the samples 3, 104 and the samples 101, 102. The comparative sample 121 exhibits substantially the same performance as the samples 104 to 120 of the present invention in terms of sensitivity, color image fastness and color reproducibility, but it is not satisfactory because the storability of the light-sensitive material is poor. In particular, the precursor releasing compound of the development inhibitor represented by the general formula (I) of the present invention and the general formula (A)
Samples 101 to 103 have a great effect on improving the above-mentioned various performances when the combined use of the dyes represented by
This is apparent when the sample 104 is compared with the sample 104. further,
The composition of the yellow filter layer has a gelatin coating amount of 0.
Sample 104 manufactured in exactly the same manner, except that the amounts were changed to 65 g / m ² , 0.50 g / m ² , and 0.40 g / m ² .
Comparing 119 and 120, it can be seen that even if the gelatin coating amount is reduced, there is no change in the above-mentioned various performances, they can be easily reduced, and good performance is maintained.

Further, the amount of residual silver in the sample obtained by subjecting the samples 101 to 120 to uniform exposure and subjecting to the above-mentioned treatment was examined by fluorescent X-ray analysis. Samples 104-120 using the dyes represented are Sample 1
It was confirmed that the residual silver amount was smaller than that of Sample Nos. 01 to 102, and was smaller than that of Sample 103.

Example 2 Cyan couplers IIC-7 and IIC-34 used in the third to fifth red-sensitive emulsion layers of Sample 120 prepared in Example 1.
And III C-2 were replaced with other couplers represented by the general formulas (II) and (III) of the present invention shown in Table 10 in equimolar amounts to prepare Samples 201 to 205. Sample 206
Is also prepared by replacing the couplers (a) to (c) shown in Table 10 with equimolar amounts. For the comparison coupler,
6 shows.

[0247]

[Chemical 86]

The produced samples 201 to 206 were subjected to the color development processing shown below together with the sample 120, and the performance of the cyan color image was examined in the same manner as in Example 1. In the treatment, the same running treatment as in Example 1 was performed and then performed.

(Treatment Method) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 10 liters Bleach 3 minutes 00 seconds 38 ° C 25 ml 20 liters Water wash 30 seconds 24 ° C 1200 ml 10 liters Settlement 3 minutes 00 seconds 38 ℃ 25 ml 10 liters Washing with water (1) 30 seconds 24 ℃ From (2) to (1) 10 liters countercurrent piping system Washing with water (2) 30 seconds 24 ℃ 1200 ml 10 liters Stability 30 Second 38 ℃ 25ml 10l Dry 4 minutes 20s 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the processing liquid will be described. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediamminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 Milliliter 4.0 Milliliter Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixer) Tank solution (g) Replenisher (g) Ethylenediamminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320.0 ml 1.0 liter 1.0 by adding water Liter pH 6.7 7.0

(Stabilizing Solution) Common to Tank Solution / Replenishing Solution (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2 1,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The results obtained by the treatment are shown in Table 10.

[0255]

[Table 10]

From the results of Table 10, Sample 12 represented by the general formula (II) or (III) of the present invention as a cyan coupler is shown.
Nos. 0, 201 to 205 are slightly different in color turbidity as compared with the sample 206 using the couplers (a) to (c) other than the coupler represented by the general formula (II) or (III),
It is clear that the photographic sensitivity, the storability of the light-sensitive material with time, and the color image fastness are excellent, and the use of the cyan coupler of the general formula (II) or (III) is preferable.

Example 3 Samples 101 to 121 prepared in Example 1 and Example 2,
No. 201 to 206, and the color developing agent 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate used in the color developer of the color developing process, which was also used in Example 1. , 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline sulfate was replaced in an equimolar amount, and only the color development time was shortened from 3 minutes 5 seconds to 2 minutes 30 seconds. The treatment was carried out without any change, and the performance was evaluated according to the method of Example 1, and Samples 101 to 121 were magenta color images for Sample 201.
.About.206 investigated the performance for cyan images. Further, the MTF value at which the density of the magenta color image obtained by exposing the MTF measurement pattern with white light and giving a density of +1.5 is given as "The Theory of the Photographi".
c Process ”, 4th Ed., (published by Macmillan, James) and measured for sharpness. The results are shown in Tables 11-12.

[0258]

[Table 11]

[0259]

[Table 12]

From the results of Tables 11 to 12, samples 104 to 120 and samples 201 to 2 using the compound represented by the general formula (I) and the dye represented by the general formula (A) of the present invention are shown.
No. 06 shows performances superior to those of Comparative Samples 101 to 103 and 121 in photographic sensitivity, storability of photosensitive material over time, color image fastness, color turbidity and sharpness. Further, in comparison with the results of Example 1 above, in the processing in which the color developing agent was changed and the color development time was shortened, particularly, the sensitivity, the color image fastness,
The color haze results give rather good results. Regarding the sharpness as well, when the treatment of Example 1 is performed and compared, it can be confirmed that the sample subjected to the treatment of this Example is also excellent in sharpness. The cyan coupler showed the same tendency as the result of Example 2, and the general formula (II) or (III) of the present invention was used.
It can be seen from the comparison between Samples 201 to 205 and Sample 206 that the coupler represented by the formula (4) is particularly preferable in terms of photographic sensitivity and color image fastness.

Example 4 Samples 101 and 104 prepared in Example 1 and Example 2,
Japanese Patent Publication No. 2-326 for 108, 114, 120 and 206
A film unit with a lens was produced in accordance with the method described in No. 15, No. 3-39784. Using these 6 types of film units with lenses, various subjects were photographed under the same conditions, and color development processing was performed with an automatic processor FP-560B AL (manufactured by Fuji Photo Film Co., Ltd.),
Next, using Fuji Mini Lab Champion, Printer Processor FA-140 (manufactured by Fuji Photo Film Co., Ltd.), Fuji Color Paper, Super FA, Type II
Printed on (the color development process at this time was Cp-43
FA was used).

When the respective patterns obtained by printing from these 6 kinds of samples were observed, 5 of the samples 104, 108, 114, 120 and 206 satisfying the constitution of the present invention were observed.
It was confirmed that the prints obtained from the seeds were superior to the prints obtained from the sample 101 in the color saturation of the subject and the depiction of delicate parts of the subject, and the image quality was improved. . It was also confirmed that when the color negative photographed and subjected to the above-mentioned treatment was stored for a long period of time at 60 ° C. and 70% relative humidity, fading of the magenta color image was small and the color image fastness was excellent. In addition, although it carried out also about the sample other than the above produced in Example 1 and Example 2, it confirmed that the sample which satisfy | fills the structure of this invention can obtain the same effect as the above.

Example 5 The color developing solution used in the color developing process of Example 1 was used to prepare the color developing agent 2-methyl-4- [N-ethyl-N- (β
The amount of -hydroxyethyl) amino] aniline sulfate was 8.0 g (replenisher was 15.0 g), the amount of potassium bromide was 7.0 g (replenisher was 0 g), and the amount of diethylenetriaminepentaacetic acid was replenisher. Adjust the pH of the replenisher to 1 and 4.0 g.
2.2, the replenishment rate of the replenisher was reduced to 80 ml / m ² , the treatment temperature was 40 ° C., and the treatment was carried out using the samples prepared in Example 1 and Example 2 without any change. Then, the same performance as in Example 1 was examined. The result obtained is the same as the result of Example 1, and the sample 1 satisfying the constitution of the present invention is obtained.
04-120, samples 201-206 are comparative samples 101-
Compared with 103 and 121, good results were shown in all of sensitivity of magenta image, color image fastness, color turbidity, and storage stability of the light-sensitive material with time.

[0264]

The silver halide color photographic light-sensitive material containing the precursor releasing compound of the development inhibitor represented by the general formula (I) and the dye represented by the general formula (A) of the present invention is
It provides high photographic sensitivity, improves color image fastness, color turbidity, sharpness, and desilvering property, and improves the storage stability of the light-sensitive material over time. Therefore, it is possible to provide a silver halide color photographic light-sensitive material having high sensitivity, high image fastness, high image quality and improved storability of the light-sensitive material over time.

Claims (3)

[Claims] 1. A support having at least one photosensitive silver halide emulsion layer, containing a precursor releasing compound of a development inhibitor represented by the following general formula (I), and A silver halide color photographic light-sensitive material containing an oil-soluble dye represented by the general formula (A). Formula (I) AX In the formula, A represents a group which reacts with an oxidized product of a developing agent to release X and forms a compound soluble or decolorizable in a processing solution, and X represents a precursor of a development inhibitor. Represents a body residue. General formula (A): In the formula, X and Y each represent an electron-withdrawing group or X
Represents a 5- or 6-membered ring to which Y and Y are bonded, Ar represents a heteroaromatic ring of indole, furan, thiophene, coumarin, or pyridine, L ¹ , L ² , and L ³ each represent a methine group, and n is 0, Represents 1 or 2. 2. A silver halide color according to claim 1, which contains a coupler represented by the general formula (II) shown in the following chemical formula 2 or the general formula (III) shown in the following chemical formula 3. Photographic material. General formula (II) In the formula, R ₁ is —CONR ₄ R ₅ , —SO ₂ NR ₄ R ₅ ,
-NHCOR ₄ , -NHCOOR ₆ , -NHSO
₂ R _6, -NHCONR ₄ R ₅ or -NHSO ₂ NR
₄ R ₅ , R ₂ is a group capable of substituting on the naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X is a hydrogen atom or an aromatic primary amine developer oxidant. Respective groups that can be separated by a coupling reaction are shown. However, R
₄ and R ₅ may be the same or different and each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₆
Represents an alkyl group, an aryl group or a heterocyclic group. k
When _two or more are present, R _2's may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring.
In addition, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X which is bonded to each other via a divalent or divalent or higher valent group may be formed. General formula (III): In the formula, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom or a coupling-off group. 3. The coating amount of gelatin of the layer containing the oil-soluble dye represented by the general formula (A) is 1.5 g / m ² or less, and the gelatin coating amount is 1.5 g / m ² or less. Silver halide color photographic light-sensitive material.