JPH05333497A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color development performance of a cyan dye image and color image fastness and to improve color reproducibility and sensitivity by incorporating a specified negative type internal latent image type silver halide grains chemically sensitized to a proper depth. CONSTITUTION:The photographic sensitive material contains one of the cyan couplers represented by formula I and one of silver halide emulsion layers contains the negative type internal latent image type silver halide grains chemically sensitized to a depth of <20mg from the surface of each grain. In formula I, Za is -NH- or -CH(R3)-; each of Zb and Zc is -C(R4)= or -N=; each of R1-R3 is an electron-attractive group having a Hammett's substituent constant sigmap of >=0.20 and the sum of those of R1 and R2 is >=0.65; R4 is H or a substituent; and X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, to a negative internal latent image type emulsion having excellent color forming property, color image fastness, color reproducibility and good sensitivity. The present invention relates to a silver halide color photographic light-sensitive material contained.

[0002]

2. Description of the Related Art The exposed aromatic silver halide as an oxidant reacts with the oxidized aromatic primary amine type color developing agent and the coupler to give indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine. It is well known that a color image is formed by forming a dye and a dye similar thereto. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta and cyan dyes.

Of these, phenol or naphthol couplers are generally used for forming a cyan dye image. However, since these couplers have an unfavorable absorption in the green region, they have a serious problem of significantly reducing color reproducibility, and it is desired to solve these problems.
As a means for solving this problem, US Pat. No. 4,8
73,183, pyrazoloazoles, EP24
Cyan couplers such as 2,4-diphenylimidazoles described in 9,453A2 have been proposed. The dyes formed from these couplers have less unfavorable absorption on the short-wave side than the conventional dyes, which is preferable for color reproduction. However, these couplers cannot be said to have sufficient color reproducibility, have low coupling activity, and have extremely low fastness to heat and light,
Further, when a developing treatment is carried out using a processing solution having a weak oxidative bleaching ability or a processing solution having a tired bleaching ability (a bleaching solution or a bleach-fixing solution), a decrease in color density occurs. The above problem remains. In addition, pyrazoloimidazoles are proposed in US Pat. No. 4,728,598. These couplers had improved coupling activity, but were insufficient in terms of hue.

EP-045 is an improvement of these.
In 6226A1, pyrrolopyrazoles have been proposed. These couplers have some improvement in the fastness of the dye formed to heat and light, but further improvement in color reproducibility is desired. Further, these couplers have room for improvement in that the stability of the coupler itself is not sufficient and the color density is lowered by long-term storage of the light-sensitive material.

Further, there has been a demand for improvement in that the sensitivity of the photosensitive material is lowered when these couplers are introduced into the photosensitive material. Among them, in the silver halide photographic light-sensitive material,
An internal latent image type emulsion has been developed as a means for improving the storage stability of an emulsion and increasing the sensitivity. Various attempts have been made to further increase the sensitivity of a light-sensitive material using this internal latent image type emulsion. For example, US Pat. No. 2,696,436
Issue 3,206,313, Issue 3,917,485
Nos. 3,979,213 and 4,623,612
JP-B-43-29405 and JP-B-45-13259, a silver halide emulsion coated sample is immersed in an AgNO ₃ solution or a silver halide solvent, or after chemical sensitization during the process of producing a silver halide emulsion. A silver halide photographic emulsion or a silver halide photographic light-sensitive material having a large internal sensitivity was prepared by Ostwald ripening or by adding an AgNO ₃ aqueous solution and a soluble halogen salt aqueous solution, and it was described that the photographic properties were good. There is.

Cyan couplers generally used in silver halide color photographic light-sensitive materials are phenol type and naphthol type couplers. On the other hand, in recent years, in order to improve the color developability (coupling activity and molecular extinction coefficient of the obtained dye) of these phenol-type and naphthol-type couplers, the fastness of the obtained color image, the absorption characteristics of the color image, etc. Proposed as a new cyan coupler. For example, 3-hydroxypyridine compounds described in European Patent No. 333,185, 3H-2-dicyanomethylidene thiazoles described in European Patent No. 362,808, and JP-A No. 64-32260. 3-dicyanomethylidene-2,3-dihydrobenzothiophene-1,1-dioxides, JP-A-63-264
753 and the pyrazoloazoles described in U.S. Pat. No. 4,873,183, U.S. Pat. No. 4,818,672.
No. 4,921,783 and JP-A-3-48243.
And imidazoles described in Japanese Patent No. 30
4,001, 329,036, 374,781
And Pyrazolopyrimidones and Pyrazoloquinazolones described in JP-A No. 2-85851 and EP-A-342.
The condensed ring triazoles described in No. 637 can be mentioned. However, in a silver halide color photographic light-sensitive material using an internal latent image type emulsion, the performance of these proposed new cyan couplers cannot satisfy the above-mentioned color forming property, color image fastness and color reproducibility at the same time. However, further improvement was required for practical use. That is, the dyes produced from these couplers have unnecessary absorption in the blue and green regions, which is a major obstacle to improving color reproducibility. Further, the conventional cyan coupler has a problem that it causes an interaction with a silver halide emulsion and thus lowers the sensitivity of a light-sensitive material using an internal latent image type emulsion containing this coupler.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention provides a silver halide color photographic light-sensitive material which is excellent in cyan color image development and color image fastness, has improved color reproducibility, and exhibits good sensitivity. It is intended to be provided. A further object of the present invention is to provide a silver halide color photographic light-sensitive material using an internal latent image type emulsion, which does not cause deterioration in sensitivity even after storage.

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors to overcome such drawbacks of the conventional silver halide color photographic light-sensitive materials, the present invention contains a specific novel coupler, and In an internal latent image type silver halide emulsion, by improving the color reproducibility and preventing a decrease in sensitivity by sensitizing a very shallow interior of a depth of less than 0.02 μm from the surface of silver halide grains. Based on this finding, the present invention has been completed. That is, the present invention provides a photographic light-sensitive material having one or more silver halide emulsion layers on a support, wherein the photographic light-sensitive material has the following general formula (Ia).
Containing at least one coupler compound represented by
At least one of the silver halide emulsion layers contains negative internal latent image type silver halide grains chemically sensitized to a depth of less than 0.02 μm from the grain surface. A color photographic light-sensitive material is provided. General formula (Ia)

[0009]

[Chemical 2]

(In the general formula (Ia), Za is -NH-
Or -CH (R ₃₎ - represents, Zb and Zc each -C (R ₄₎ = or represent -N =. R ₁ , R ₂ and R ₃ each have a Hammett's substituent constant σ _p value of 0.
Represents 20 or more electron withdrawing groups. However, R ₁ and R ₂
The sum of the σ _p values of is 0.65 or more. R ₄ represents a hydrogen atom or a substituent. However, when two R _4's are present in the formula, they may be the same or different. X represents a hydrogen atom or a group which is released by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. In addition, the group of R ₁ , R ₂ , R ₃ , R ₄ or X becomes a divalent group and is bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. You may. ) Next, the compound represented by formula (Ia) will be described in detail. In the general formula (Ia),
Za represents -NH- or -CH (R ₃₎ - represents, Zb and Zc each -C (R ₄₎ = or represent -N =. Accordingly, the cyan coupler represented by the general formula (Ia) of the present invention is specifically represented by the following general formulas (IIa) to (IX).
It is represented by a).

[0011]

[Chemical 3]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and X
Are synonymous with each in the general formula (Ia). ) In the present invention, the general formula (IIa), (IIIa) or (IVa)
The cyan coupler represented by the formula (3) is preferable, and the cyan coupler represented by the general formula (IIIa) is particularly preferable.

The cyan coupler of the present invention is an electron-withdrawing group in which R ₁ , R ₂ and R ₃ are all 0.20 or more,
Moreover, the sum of the σ _p values of R ₁ and R ₂ is 0.65 or more. R
The sum of σ _p values of ₁ and R ₂ is preferably 0.70 or more, and the upper limit is about 1.8.

Each of R ₁ , R ₂ and R ₃ is an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. An electron withdrawing group having a σ _p value of 0.35 or more is preferable, and an electron withdrawing group having a σ _p value of 0.60 or more is more preferable. The upper limit is an electron-withdrawing group of 1.0 or less. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
According to the rule of thumb advocated by LP Hammett in
This is widely accepted today. There are σ _p and σ _m values for the substituent constants determined by Hammett's rule, and these values are described in many general textbooks.
For example, "De Lange's Hand book of Chemis" edited by JA Dean
try ”12th edition, 1979 (McGraw-Hill) and“ Special Issue on Chemistry ”, No. 122, pages 96-103, 1979.
Detailed in the year (Nankodo). In the present invention, R ₁ , R ₂ and R ₃ are defined by the Hammett's substituent constant σ _p value, but it does not mean that the values known from the literatures described in these publications are limited to certain substituents. Of course, even if the value is unknown in the literature, it is included as long as it falls within the range when measured based on Hammett's rule.

Specific examples of R ₁ , R ₂ and R ₃ , which are electron withdrawing groups having a σ _p value of 0.20 or more, include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Cyano group, nitro group, dialkylphosphono group, diarphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiol group Carbonyl group, halogenated alkyl group, halogenated alkoxy group,
A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, a heterocyclic group,
Examples thereof include a halogen atom, an azo group and a selenocyanate group. Among these substituents, the group capable of further having a substituent may further have a substituent as mentioned below for R ₄ .

R ₁ , R ₂ and R ₃ will be described in more detail. As electron withdrawing groups having a σ _p value of 0.20 or more, acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4- Dodecyloxybenzoyl), acyloxy group (eg acetoxy), carbamoyl group (eg carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamide) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, 2-
Decyl-hexyloxycarbonylmethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl, 2,5-amylphenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (For example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenylsulfinyl), alkyl A sulfonyl group (for example, methanesulfonyl, octanesulfonyl),
An arylsulfonyl group (eg, benzenesulfonyl,
Toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio, benzoylthio), sulfamoyl group (eg, N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (for example,
Methylthiocarbonyl, phenylthiocarbonyl), halogenated alkyl groups (eg trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg trifluoromethyloxy), halogenated aryloxy groups (eg pentafluorophenyloxy), halogens Alkylamino group (eg, N, N-di- (trifluoromethyl) amino), halogenated alkylthio group (eg, difluoromethylthio, 1,1,2,2-tetrafluoroethylthio), σ _p value An aryl group (for example, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) substituted with 0.20 or more other electron-withdrawing groups, a heterocyclic group (for example, 2-benzoxa). Zolyl, 2-benzothiazolyl, 1-phenyl-2-
Benzimidazolyl, 5-chloro-1-tetrazolyl,
1-pyrrolyl), a halogen atom (eg chlorine atom, bromine atom), an azo group (eg phenylazo) or a selenocyanate group.

Typical σ _p values of electron-withdrawing groups are cyano group (0.66), nitro group (0.78), trifluoromethyl group (0.54), acetyl group (0. 5
0), trifluoromethanesulfonyl (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred as R ₁ , R ₂ and R ₃ are an acyl group, an acyloxy group, a carbamoyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, Mention may be made of halogenated aryloxy groups, halogenated aryl groups, aryl groups substituted with two or more nitro groups, and heterocyclic groups. More preferably,
An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group.
More preferably, a cyano group, an alkoxycarbonyl group,
Aryloxycarbonyl and halogenated alkyl groups. Particularly preferably, a cyano group, a fluorine atom, an alkoxycarbonyl group substituted with an alkoxycarbonyl group or a carbamoyl group, or an alkoxycarbonyl group having a linear, branched or ether bond, unsubstituted or substituted with an alkyl group or an alkoxy group It is an aryloxycarbonyl group. As a combination of R ₁ and R ₂ , preferably, R ₁ is a cyano group and R ₂ is an alkoxycarbonyl group substituted with a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, or an alkoxycarbonyl group having a linear, branched or ether bond. It is an aryloxycarbonyl group which is substituted with a group, unsubstituted or an alkyl group or an alkoxy group.

R ₄ represents a hydrogen atom or a substituent (including atoms), and the substituent is a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, Alkyl / aryl or heterocyclic thio group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, alkylamino group, arylamino group, ureido group, sulfamoylamino group, alkenyloxy group, formyl group, Alkyl / aryl or heterocyclic acyl group, alkyl / aryl or heterocyclic sulfonyl group,
Alkyl / aryl or heterocyclic sulfinyl group, alkyl / aryl or heterocyclic oxycarbonyl group,
Alkyl / aryl or heterocyclic oxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, phosphonyl group, sulfamide group, imide group,
Azolyl group, hydroxy group, cyano group, carboxy group,
Examples thereof include a nitro group, a sulfo group and an unsubstituted amino group. The alkyl group, aryl group or heterocyclic group contained in these groups may be further substituted with the substituents exemplified for R ₄ .

More specifically, R ₄ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an aliphatic group (eg, a straight chain or branched chain alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), an aryl group (preferably having 6 to 36 carbon atoms, for example, phenyl, naphthyl, 4-hexadecoxyphenyl,
4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, 3- (2,4
-Tert-amylphenoxyacetamido) phenyl),
Heterocyclic groups (eg, 3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), alkoxy groups (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2 -Methanesulfonylethoxy), aryloxy groups (eg phenoxy, 2-methylphenoxy, 4-te
rt-Butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), heterocyclic oxy A group (eg 2-benzimidazolyloxy, 1-phenyltetrazole-5-oxy, 2
-Tetrahydropyranyloxy), an alkyl aryl or a heterocyclic thio group (for example methylthio, ethylthio, octylthio, tetradodecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4
-Tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-tert-octylphenylthio,
3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,4-triazole-6-thio, 2-pyridylthio), acyloxy group (eg acetoxy, hexadecanoyloxy), carbamoyloxy group (eg N-ethylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg trimethylsilyl) Oxy, dibutylmethylsilyloxy), a sulfonyloxy group (eg, dodecylsulfonyloxy), an acylamino group (eg, acetamide, benzamide, tetradecanamide, 2- (2,4-tert-amylphenoxyacetamide), 2- [4- (4- (4- (Hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide) , An alkylamino group (eg, methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, methylbutylamino), an arylamino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidoanilino,
N-acetylanilino, 2-chloro-5- [α-2-te
rt-Butyl-4-hydroxyphenoxy) dodecanamide] anilino, 2-chloro-5-dodecyloxycarbonylanilino), a ureido group (eg methylureido,
Phenylureido, N, N-dibutylureido, dimethylureido), sulfamoylamino group (eg N, N
-Dipropylsulfamoylamino, N-methyl-N-
Decylsulfamoylamino), alkenyloxy group (eg 2-propenyloxy), formyl group, alkyl aryl or heterocyclic acyl group (eg acetyl, benzoyl, 2,4-di-tert-amylphenylacetyl, 3-phenyl) Propanoyl, 4-dodecyloxybenzoyl), alkyl aryl or heterocyclic sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl group (for example, octansulphinyl, dodecylsulfinyl, dodecanesulfinyl, dodecanesulfinyl, phenyl) Sulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), an alkyl aryl or a heterocyclic oxycarbonyl group (eg methoxy) Cycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), an alkyl aryl or a heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino,
Phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5) -Tert-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N- Ethyl- -Dodecylsulfamoyl, N, N-diethylsulfamoyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), sulfamide group (eg dipropylsulfamoylamino), imide group (eg N -Succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy group, cyano group, carboxy group, nitro group , A sulfo group, and an unsubstituted amino group.

R ₄ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino. Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Examples thereof include sulfinyl group, phosphonyl group, acyl group and azolyl group. More preferably an alkyl group or an aryl group, more preferably at least one alkoxy group, a sulfonyl group, a sulfamoyl group,
It is an alkyl group or an aryl group having a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent.

In the general formula (Ia), X is a hydrogen atom or a group which leaves when the coupler reacts with an oxidized product of an aromatic primary amine color developing agent (hereinafter, simply referred to as "leaving group"). ) And X represents a leaving group, the leaving group may be a halogen atom, an aromatic azo group, oxygen.
An alkyl group, an aryl group or a heterocyclic group, which binds the coupling position via nitrogen / sulfur or a carbon atom,
An alkyl or aryl sulfonyl group, an aryl sulfinyl group, an alkyl aryl or a heterocyclic carbonyl group, or a heterocyclic group bonded to a coupling position at a nitrogen atom, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl Alternatively, an arylsulfonyloxy group, an acylamino group, an alkyl or aryl sulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl aryl or a heterocyclic thio group, a carbamoylamino group, an arylsulfonyl group, an arylsulfonyl group, and a 5-membered group. Alternatively, there are 6-membered nitrogen-containing heterocyclic groups, imide groups, arylazo groups, etc., and the alkyl group, aryl group or heterocyclic group contained in these leaving groups is R ₄
May be further substituted with the substituents described above, and when these substituents are two or more, they may be the same or different, and these substituents further have the substituents listed for R _4. Good.

More specifically, the leaving group is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonyl). Methoxy), an aryloxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), an acyloxy group ( For example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino (E.g., di-chloroacetyl amino, heptafluorobutyryl amino), alkyl or aryl sulfonamido group (e.g., methanesulfonic amino, trifluoromethanesulfonic amino, p
-Toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy),
Alkyl-aryl or heterocyclic thio groups (eg,
Ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), arylsulfonyl group (for example, 2-butoxy-5-tert-octylphenylsulfonyl), arylsulfinyl group (for example, 2-butoxy-5-tert-
Octylphenylsulfinyl), a carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2- Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. Of course, these groups may be further substituted with the groups listed as the substituent for R ₄ . Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. .. More preferably, it is an arylthio group.

In the cyan coupler represented by the general formula (Ia), a group represented by R ₁ , R ₂ , R ₃ , R ₄ or X has the general formula (Ia).
a) containing a cyan coupler residue represented by a) to form a dimer or higher multimer, R ₁ , R ₂ ,
The group of R ₃ , R ₄ or X may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is represented by the general formula (I
A typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a cyan coupler residue represented by a). In this case, one or more types of cyan color-forming repeating units having a cyan coupler residue represented by the general formula (Ia) may be contained in the polymer, and as a copolymerization component, acrylic acid ester, methacrylic acid ester, maleic acid, etc. It may be a copolymer containing one or more non-color-forming ethylene type monomers that do not couple with the oxidation products of aromatic primary amine developers such as esters. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 4]

[0026]

[Chemical 5]

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical formula 12]

The compounds of the present invention and intermediates thereof can be synthesized by known methods. For example, J. Am. Chem. Soc., 80, 5332 (1958), J.
Ame. Chem., 81, 2452 (1959), J. Am. Chem.
Soc., 112, 2465 (1990), Org.Synth., I
270 (1941), J. Chem. Soc., 5149 (196).
2), Hetrocyclic., 27, 2301 (1988),
Rec.Trav.chim., 80, 1075 (1961) and the like, or the literature cited therein or a similar method. Next, a specific synthesis example will be shown. (Synthesis Example 1) Synthesis of Exemplified Compound (9) Exemplified Compound (9) was synthesized by the following route.

[0035]

[Chemical 13]

2-Amino-4-cyano-3-methoxycarbonylpyrrole (1a) (66.0 g, 0.4 mol)
In dimethylacetamide (300 ml) at room temperature, 3,5-dichlorobenzoyl chloride (2a) (8
3.2 g, 0.4 mol) is added and stirred for 30 minutes. Add water and extract twice with ethyl acetate. The organic layers are collected, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and acetonitrile (300 ml)
When recrystallized from compound (3a) (113 g, 84
%) Was obtained.

Powder of potassium hydroxide (252 g, 4.5 mol) was added to a solution of (3a) (101.1 g, 0.3 mol) in dimethylformamide (200 ml) at room temperature, and the mixture was stirred well. Under cooling with water, hydroxylamine-O-sulfonic acid (237 g, 2.1 mol) was added little by little, taking care not to raise the temperature rapidly, and the mixture was stirred for 30 minutes after the addition. A 0.1N hydrochloric acid aqueous solution is added dropwise to neutralize while observing the pH test paper. Extract three times with ethyl acetate, wash the organic layer with water and saturated brine, and dry over anhydrous sodium sulfate.
The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent, hexane: ethyl acetate = 2: 1) to give compound (4a) (9.50 g, 9%).

Carbon tetrachloride (9c) was added to a solution of (4a) (7.04g, 20mmol) in acetonitrile (30ml) at room temperature.
c) was added, followed by triphenylphosphine (5.76).
g, 22 mmol) and heated to reflux for 8 hours. After cooling, water is added and the mixture is extracted 3 times with ethyl acetate. The organic layer is washed with water and saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4: 1) to obtain (5a) (1.13 g, 17%).

1.8 g of the obtained (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane, and further 1.5 g
Of titanium isopropoxide was added. After keeping the reaction temperature at 110 ° C. and reacting for 1.5 hours, ethyl acetate was added and the mixture was washed with water. The ethyl acetate layer was dried, evaporated, and purified by residue column chromatography to obtain 1.6 g of the desired exemplary compound (9). Melting point is 9
It was 7-98 degreeC.

The compound represented by formula (Ia) of the present invention is 1.0 to 1.0 × 1 per mol of silver halide.
It can be used in the range of 0 ^-3 mol. It is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol.

In the present invention, when the compound represented by the general formula (Ia) is used as the main coupler, it is preferably added to the red-sensitive silver halide emulsion layer or the non-photosensitive layer adjacent thereto. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

In the present invention, the compounds represented by formula (Ia) may be used in combination of two or more kinds, or may be used in combination with other known couplers.

In the present invention, the compound represented by formula (Ia) can be introduced into the color light-sensitive material by various known dispersion methods.

In the present invention, the compound represented by the general formula (Ia) can be dispersed by using a high boiling point organic solvent. As a high boiling organic solvent, the melting point at normal pressure is 17
It is preferably 5 ° C or higher.

The internal latent image type emulsion of the present invention needs to be chemically sensitized to a depth of less than 0.02 μm from the grain surface. When the position 0.02 μm or more from the surface is chemically sensitized, the black and white / color negative / color reversal light-sensitive material is not sufficiently developed even if it is developed with a practical developer, resulting in substantial loss of sensitivity. In addition, the effect of the addition of the tellurium compound of the present invention is not remarkable. The above-mentioned practical developing solution means a developing solution from which a silver halide solvent is intentionally removed so as to develop only a surface latent image, or a large amount of silver halide intended to develop an internal latent image. Instead of a developing solution containing a solvent, it contains a silver halide solvent capable of exhibiting optimum sensitivity by causing a reduction reaction while appropriately dissolving silver halide. However, if the solvent is contained in a large amount, the silver halide is excessively dissolved during the processing, and the graininess is deteriorated by infectious development, which is not preferable. Specifically, it is preferable that the developer contains 100 mg / liter or less and 20 mg / liter or more of potassium iodide or 100 g / liter or less and 20 mg / liter or more of sodium sulfite or potassium sulfite as a silver halide solvent. In addition, potassium thiocyanate or the like can be used as a silver halide solvent in the developing solution.

The more preferable position of the chemically sensitized portion is 0.002 μm or more and less than 0.015 μm, and more preferably 0.004 μm or more and less than 0.01 μm. Further, more preferably, it is necessary to pay attention not only to the site to be chemically sensitized, but also to the latent image distribution in the grain including the ratio of the surface sensitivity to the internal sensitivity. In this case, the latent image distribution in the particle generated by exposure has at least one local maximum value inside the particle, the position where this one local maximum value exists is less than 0.01 μm from the particle surface, and the particle surface also has the above-mentioned value. Most preferably, it is chemically sensitized so that it is 1/5 or more and less than 1 time the maximum value.

Here, the latent image distribution is the depth of the latent image from the particle surface (x μm) on the horizontal axis and the number of latent images (y) on the vertical axis, where x is

[0048]

[Equation 1]

S: average grain size (μm) of silver halide emulsion Ag ₁ : residual silver amount after unexposed emulsion coating sample is subjected to the following treatment Ag ₀ : coating silver amount before treatment, and y After 1/100 second white exposure,
It is the reciprocal of the exposure amount that gives a density of fog + 0.2 when the following process is performed. The processing conditions for obtaining the latent image distribution are as follows: N-methyl-p-aminophenol sulfate 2.5 g L-sodium ascorbate 10 g sodium metaborate 35 g potassium bromide 1 g Water added 1 liter (pH 9.6). Sodium thiosulfate is added to the treatment liquid in an amount of 0 to 10 g / liter and treated at 25 ° C. for 5 minutes. By changing the amount of sodium thiosulfate from 0 to 10 g / liter, the depth from the surface of the latent image in the silver halide grains developed during processing is changed, and the number of latent images in the depth direction is changed. You can know the change of.

A method for preparing an internal latent image type emulsion is described in US Pat. Nos. 3,979,213, 3,966,476, 3,206,313, 3,917,485 and JP-B-43. No. 29405, No. 45-13259 and the like can be used. In any method, a chemical sensitization method or a chemical sensitization method is used to obtain an emulsion having a latent image distribution of the present invention. The amount of silver halide precipitated after chemical sensitization and the conditions of precipitation must be adjusted. That is, U.S. Pat. No. 3,966,476 also implements a method of precipitating silver halide beyond the emulsion grains after chemical sensitization by the control double jet method. However, when chemically sensitized silver halide is precipitated by the method as practiced in this patent, the photosensitive nuclei cannot be embedded inside the grain. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after the chemical sensitization is larger than that carried out in U.S. Pat. No. 3,966,476 and the precipitation conditions ( For example, it is necessary to control the solubility of silver halide in the precipitation and the rate of adding the soluble silver salt and the soluble halogen salt) so that the thickness is less than 0.02 μm.

Further, in US Pat. No. 3,979,213, an internal latent image type emulsion is prepared by a method of reprecipitating silver halide on the emulsion grains whose surfaces are chemically sensitized by the control double jet method. . If the amount of silver halide practiced in this patent were to be precipitated on the grains, the ratio of surface sensitivity to total sensitivity would be less than one tenth. Therefore, the amount of silver halide precipitated after chemical sensitization should be less than that practiced in U.S. Pat. No. 3,979,213 for the most favorable latent image distribution.

Among the internal latent image type emulsions of the present invention, the most preferable one is a photographic emulsion having a step of forming a shell on a silver halide core grain as described in Japanese Patent Application No. 1-1150728. In the method, it can be obtained by a method for producing a silver halide photographic emulsion, which comprises chemically sensitizing the core grains and then forming a shell in the presence of a tetrazaindene compound. In this method, the tetrazaindene-based compound is used in a dispersion system in which seed grains and / or silver halide grains growing with seed grains as nuclei are dispersed, that is, in the emulsion in an amount of 10 per 1 mol of silver halide contained in the emulsion. It is preferably present in the range of ^-2 to 10 ^-5 mol, more preferably 10 ^-2 to 10 ^-5.
-4 mol range. The addition amount of the tetrazaindene-based compound has a great influence on the latent image distribution from the surface of the silver halide grain to the inside thereof, but the optimum amount thereof is the halogen composition of the emulsion grains and the precipitation of silver halide in the core, that is, the core. Is appropriately increased or decreased within the above-mentioned addition amount range depending on pAg, pH, temperature and the like when further growing.

For example, a large amount of Ag used for shell formation,
When the number of latent images on the shell surface is small, it is preferable to add a larger amount of the tetrazaindene compound in the above addition amount range, but on the other hand, the amount of Ag used for shell formation is small and the number of latent images on the shell surface is large. When it tends to occur, it is preferable to add a smaller amount. The tetrazaindene-based compound may be added directly to a water-soluble protective colloid solution containing seed particles, and the tetrazaindene-based compound may be dissolved in a water-soluble silver halide aqueous solution to form seed particles as a nucleus. It is also possible to gradually add it as it grows. The tetrazaindene-based compound may be present at the time of further grain growth from the core grain, and may be added before the chemical sensitization of the core. In particular, the tetrazaindene compound is adsorbed on the silver halide grains and has a function of specifying the site to be chemically sensitized, and therefore it is preferable that the compound is present even during the chemical sensitization of the core.

In the present method, the amount of silver used in the step of forming a shell on the chemically sensitized core and the amount of silver (M) in the shell portion preferably satisfy the following general formula. That is,

[0055]

[Equation 2]

M ₀ : Silver amount of seed particles R: Final particle size (μ) The silver potential (SCE) in the step of forming the shell on the core particles in this method is +80 mV or less, −30 mV.
The above is preferable. When it is higher than +80 mV, the chemical sensitizer which is not used during the chemical sensitization during the shell formation process easily reacts with the shell portion, so that the surface sensitivity is made higher than the internal sensitivity. Also,
When the shell formation on the core particles is performed at less than -30 mV,
The chemically sensitized core particle surface undergoes an oxidation reaction due to excess halogen, resulting in a decrease in sensitivity. A more preferable silver potential in the step of growing the core particles is −10 mV or higher, +60.
It is mV or less.

In the present invention, the temperature in the step of forming the shell on the core particles is preferably + 70 ° C. or lower, + 35 ° C. or higher. When the temperature is higher than + 70 ° C., the residual chemical sensitizer easily reacts with the shell portion as described above, so that the surface sensitivity cannot be lower than the internal sensitivity. Further, when the core grains are grown below + 35 ° C., new nuclei are likely to be generated during the crystal growth process, and new silver halide is not sufficiently precipitated on the chemically sensitized site of the core grains. That is, new nuclei are likely to be generated in the shell forming step, which is not preferable. A more preferable temperature in the shell forming step is 45 ° C. or higher and 60 ° C. or lower. In the present invention, the addition rate of the water-soluble silver salt solution in the grain growth step from the core grain is preferably within the range of 30 to 100% of the crystal growth critical rate. What is the critical speed of crystallization?
It is defined as the upper limit at which new nuclei are not substantially generated in the process of grain growth. In addition, the term "substantially not generated" means that the weight of newly generated crystal nuclei is preferably 1 of the total silver halide weight.
It means 0% or less.

In the present invention, the chemical sensitization of the core particles is performed by TH James, The Theory of Photographic Process, 4th edition, published by Macmillan, 1977 (TH James, The Theory). of the P
hotographic Process, 4thed, Macmillan, 1977) 67
~ Research Disclosure 1 can be carried out using activated gelatin as described on pages 76-76.
Volume 20, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 1345.
2, U.S. Pat. Nos. 2,642,361 and 3,297,
No. 446, No. 3,772, 031, No. 3,857, 7
No. 11, No. 3,901,714, No. 4,266,01
8 and 3,904,415, as well as several combinations of sulfur, selenium, tellurium, gold, platinum, iridium as described in GB 1,315,755. In the most preferred embodiment, the silver potential (SCE) is ± 0 mV or more and +120 mV or less, more preferably +30 mV or more and +120 mV or less, and further preferably +60 mV or more and +120 mV or less. Increasing the silver potential, ie, pulling pAg, not only obtains good sensitivity by effectively promoting the chemical sensitization reaction, but also reduces the residual chemical sensitizer remaining even during the formation of the shell. , Which is preferable because the surface sensitivity is lower than the internal sensitivity.

In the present invention, the layer containing the internal latent image type emulsion is not particularly limited, but a red-sensitive emulsion layer is preferable, and it is preferably contained in the same layer as the cyan coupler represented by the general formula (I). The latent image ratio formed on the surface of the internal latent image type emulsion is preferably 0.1 to 0.
8, more preferably 0.2 to 0.7. Further, the silver halide color photographic light-sensitive material of the present invention is preferably subjected to a developing treatment with a developing solution containing a silver halide solvent to form an image. The silver halide color photographic light-sensitive material of the present invention is preferably a silver halide color reversal light-sensitive material.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer 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 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of 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. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, 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) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63
As described in Japanese Patent No. 936, the blue-sensitive layer / 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 sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. 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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
No. 663,271, No. 4,705,744, No. 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms 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
Fine particles of 0.2 micron or less or large size particles having a projected area diameter of up to about 10 microns may be used, and a polydisperse emulsion or a monodisperse emulsion may be used. The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and
No.18716 (November 1979), p. 648, ibid. No. 307105 (1989
Nov.), pp.863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Glafkides, Chemie).
et Phisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 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 in Gutoff, Photographic Science and E.
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure.
Further, silver halides having different compositions may be joined by epitaxial joining, and, for example, rhodan silver,
It may be bonded to a compound other than silver halide such as 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 is formed inside the grain, or a type which has a latent image on both the surface and the inside.
It must be a negative emulsion. 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 the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure N
It is described in o.17643, No.18716 and No.307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, grain size distribution, halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer. U.S. Pat.No. 4,082,553 described in US Pat. It can be preferably used for a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain having a fogged grain inside or on its surface is described in U.S. Pat.
98, JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, and particularly preferably 0.05 to 0.6 μm. The particle shape is not particularly limited,
It may be regular grains, or a polydisperse emulsion,
Monodispersion (wherein at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size) is preferred. In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a 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 developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferably silver iodide is 0.5
-10 mol% is contained. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area) of 0.01
˜0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain 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 the layer containing the fine grain silver halide grains. 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, pages 23 to 24, page 648, right column 866 ... Page 868 Supersensitizer to page 649 Right column 4. Whitening agent page 24 Page 647 Page right column 868 page 5. Fogging prevention 24 to page 649 Page right column 868 to 870 page Agent and stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dyes, ultraviolet absorbers, 7. stain, page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25, page 650, left Column 872 Stabilizer 9. Hardener page 26 651 page left column 874 to 875 page 10. Binder page 26 page 651 page left column 873 to 874 page 11. Plasticizer, page 27 page 650 right column page 876 lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static, page 27, page 650, right column, pages 876 to 877, inhibitor, matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of fixing by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. .. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog 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, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure Nos. 17643, VII-CG, and Nos. 307105, VII.
-C to G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, No. 1,476,760, and U.S. Patent No. 3,97.
Those described in 3,968, 4,314,023, 4,511,649, European Patent 249,473A and the like 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 73,63 are preferred.
6, US Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No.2
4230 (June 1984), JP-A-60-43659, 61-72238
No. 60, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Pat.Nos. 4,500,630, 4,540,654, 4,5
Those described in 56,630, International Publication WO88 / 04795 and the like are particularly preferable. Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 12, No. 4,146,396, No. 4,228,233, No. 4,2
No. 96,200, No. 2,369,929, No. 2,801,171, No.
2,772,162, 2,895,826, 3,772,002,
No. 3,758,308, No. 4,334,011, No. 4,327,173
No. 3, West German Patent Publication No. 3,329,729, European Patent No. 121,365
A, No. 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559.
No., No. 4,427,767, No. 4,690,889, No. 4,25
Those described in 4,212, 4,296,199 and JP-A-61-42658 are preferable. Further, JP-A-64-553 and 64-64
The pyrazoloazole-based couplers described in JP-A-554, 64-555 and 64-556, 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 described in US Pat.
No. 51,820, No. 4,080,211, No. 4,367,282, No.
4,409,320, 4,576,910, British patent 2,102,137
And European Patent No. 341,188A. Examples of couplers in which the coloring dye has an appropriate diffusibility include U.S. Pat.No. 4,366,237, British Patent No. 2,125,570, European Patent No.
Those described in 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No. 1
7643, VII-G, No. 307105, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also, U.S. Pat.
And a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat.
It is also preferable to use a coupler having a dye precursor group as a leaving group capable of reacting with a developing agent to form a dye as described in 4,777,120. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are
RD 17643, Item VII-F and No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
Nos. 4,248,962 and 4,782,012 are preferable. RD No. 11449, 24241, JP 61
-The bleaching accelerator releasing couplers described in 201247 etc. are effective in shortening the processing time having a bleaching ability,
In particular, the effect is great when it is added to the light-sensitive material using the above-mentioned tabular silver halide grains. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patents 2,097,140 and 2,131,188 and JP-A-59-157638 and 59-170840 are preferable. Further, by a redox reaction with an oxidized product of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and 1-45687, a fogging agent and a development accelerator. ,
A compound that releases a silver halide solvent or the like is 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 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 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, bisyl 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) and 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 with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. 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, and 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. 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, particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2 days)
The film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 vol., No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 90% of the maximum swollen film thickness reached when treated at ℃ for 3 minutes and 15 seconds is defined as the saturated film thickness and defined as the time required to reach 1/2 of the saturated film thickness.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm. 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 preferably 150 to 500%.

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 the 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-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-
Hydroxypentyl) 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, Examples thereof include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. 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-toluenesulphonates or sulphates are preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include an inhibitor or an antifoggant. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N- tetramethylenephosphonic acid, ethylenediamine-
Representative examples are di (o-hydroxyphenylacetic acid) and salts thereof.

Next, processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) color development-bleaching-fixing-washing-stable 9) color development-bleaching-bleach-fixing-washing-stable 10) color development-bleaching-bleach-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color development-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stabilizing In the processing steps 4) to 15), the washing step immediately before the stabilizing step may be omitted, or conversely the stabilizing step of the final step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black-and-white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-).
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 67,872 can be used alone or in combination. In the black and white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (eg, Hydroxides, carbonates), dissolution tablets (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid),
Sensitizer (for example, quaternary ammonium salt), development accelerator,
A surfactant, a defoaming agent, a film hardening agent, a viscosity imparting agent, etc. can be contained. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and the sulfite salt added as the above preservative usually plays a role. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂
O, etc. _{5, K 2 S 2 O 3} , Na 2 S 2 O 3 can be mentioned. The pH value of the developer thus adjusted is selected to a level that provides the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to carry out the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed,
Generally, it is 3 liters or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and 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 cover 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 development processing 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 reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These processes may be carried out immediately after color development without passing through other processing steps,
In order to prevent unnecessary post-development, air fogging, and to reduce the amount of color developing solution brought into the desilvering process, and to the photosensitive material such as sensitizing dyes and dyes contained in the photographic light-sensitive material In order to wash out the impregnated color developing agent and render it harmless, it may be subjected to a bleaching treatment or a bleach-fixing treatment after a processing step such as stopping, adjusting and washing with water after the color developing treatment.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. 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. 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. Among them, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III)
II) Complex salts and other aminopolycarboxylic acid iron (III) complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in 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 can be used for speeding up the processing. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,89
3,858, West German Patents 1,290,812, 2,059,988,
JP53-32736, JP53-57831, JP53-37418, JP53
-72623, 53-95630, 53-95631, 53-104232
No. 53, No. 124424, No. 53-141623, No. 53-28426,
Research Disclosure No.17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, and JP-A-53
-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent 1,127,715, JP 58-16,235; iodide salts; West German Patents 966,410, 2,748,430.
Compounds described in Japanese Patent Publication No. 45-883
Polyamine compounds described in No. 6; Others JP-A-49-40,943
No. 49, 59-644, 53-94,927, 54-35,727.
Nos. 55-26,506 and 58-163,940; 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-53-95,630 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 photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound 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. Use of thiosulfates Is generally used, and ammonium thiosulfate is most widely used. 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 EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 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 strengthened as much as possible. As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process 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 system such as countercurrent, forward flow, and other various 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 a
nd Television Engineers Volume 64, P. 248-253 (1955)
May May issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly 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. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, edited by Sanitary Technology, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40 ° C 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 stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization 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. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include 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 above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In processing using an automatic processor,
When each of the above treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

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 U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
99, Research Disclosure 14,850 and 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A-56-64339, JP-A-57-144547,
And No. 58-115438, etc. Various treatment liquids in the present invention are used at 10 ° C to 50 ° 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.

[0081]

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 (1) Preparation of emulsion a. Emulsion A 15% AgNO ₃ aqueous solution 800 cc and KBr while keeping pH 6.8 and silver potential (SCE) +60 mV in a 1,560 cc 3.4% gelatin aqueous solution kept at 75 ° C.
KI is 0.85 mol / liter and 0.03, respectively.
An aqueous solution containing 1 mol / liter was added by a double jet for 60 minutes to prepare monodisperse cubic core particles having a ridge length of 0.35 μm. Next, 1.8 mg of Compound A-5 was used as a sulfur sensitizer in the core particles, and sodium chloroaurate was used as a gold sensitizer, and Compounds A-2 and A-.
1.1 mg, 4.0 mg, 0.3 mg of 3 were added, respectively,
Chemical sensitization was carried out for 60 minutes at pH 6.8 and silver potential +80 mV. Here, 0.14 g each of the compounds A-1 and A-4,
After adding 0.3g, lower the temperature to 50 ℃ and re-add 15%
An aqueous solution containing 200 cc of AgNO ₃ aqueous solution, 0.85 mol / liter of KBr and 0.031 mol / liter of KI was added over 5 minutes at pH 6.8 and silver potential of +10 mV to precipitate the shell, and the average edge of the final particles. Length is 0.38 μm, average silver iodide content is 3.5 mol%
Cube monodisperse particles of were obtained. The soluble silver salt was removed by a conventional flocculation precipitation method to obtain an internal latent image type emulsion (emulsion A) having a final pH of 6.2 and a pAg of 8.4. Coefficient of variation of the grain size (ridge length) distribution of this emulsion (value obtained by dividing the standard deviation of the distribution by the average value and multiplying by 100)
Was 8%, and the variation coefficient of the silver iodide content distribution was 5%.
Alternatively, the particles obtained here have a (100) plane of 92%,
The (111) plane had a crystal habit of 8%. In addition, Table 1 shows the ratio of the latent image formed on the surface of the particles, which is determined by the method described in the text.

[0083]

[Chemical 14]

[0084]

[Table 1]

B. Emulsions B to E AgNO used for core formation and shell formation in Emulsion A
Internal latent image type emulsions (emulsions B to E) having different depths from the grain surface to the chemically sensitized position as shown in Table 7 were prepared by changing the ratio of the ₃ aqueous solutions. c. Emulsion F The conditions for forming a shell in Emulsion A are as follows:
An internal latent image type emulsion (Emulsion F) in which the ratio of the latent image formed on the surface was higher than that of the emulsion A was obtained by setting the temperature to 60 ° C. and the silver potential to 60 mV. d. Emulsion G The conditions for forming a shell in Emulsion A were set to a temperature of 40.
The internal latent image type emulsion (Emulsion G) in which the ratio of the latent image formed on the surface was smaller than that of the emulsion A was obtained by increasing the addition rate of the aqueous AgNO ₃ solution to 5 ° C. at a silver potential of −30 mV. e. Emulsion H Sulfur sensitizer added after core grain formation in Emulsion A,
The gold sensitizer and the compounds A-1, A-2, A-3, and A-4 were not added before the formation of the shell, but were added after the formation of the shell and the removal of the soluble silver salt to chemically sensitize the shell surface. A surface latent image type emulsion (emulsion H) was obtained by carrying out. At this time,
Optimum sensitivity was achieved by adding 1.2 times the sensitizer to Emulsion A. (2) Preparation of coating sample A multilayer color light-sensitive material comprising layers of the following compositions was prepared on a 127 µm-thick cellulose triacetate film support which was undercoated, and was designated as Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil -3 0.1 g Dye D-4 0.4 mg Third layer: intermediate layer Fine grained silver iodobromide emulsion with surface and inside fogged (average grain size 0.06 μm, variation coefficient 18%, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion 1 Silver amount 0.1 g Emulsion B (Emulsion B of Example 1) Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15g Coupler C-2 0.05g Coupler C-3 0.05g Coupler C-9 0.05g Compound Cpd-C 10mg High boiling point organic solvent Oil-2 0.1g Additive P-1 0.1g

Fifth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Emulsion B (Emulsion B of Example 1) Silver amount 0.2 g Emulsion 2 Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion 3 Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd -I 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0.002 g UV absorber U-5 0.01 g Dye D-1 0.02 compound Cpd-C 5 mg compound Cpd-J 5 mg compound Cpd-K 5mg High boiling point Dot organic solvent Oil-1 0.02g

Eighth layer: intermediate layer Silver iodobromide emulsion with surface and internal fog (average particle size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1. 0g Additive P-1 0.2g Color mixing inhibitor Cpd-A 0.1g 9th layer: low sensitivity green sensitive emulsion layer Emulsion 4 Silver amount 0.1g Emulsion 5 Silver amount 0.2g Emulsion 6 Silver amount 0.2g Gelatin 0.5 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.20 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High-boiling point organic solvent Oil-1 0.1g High-boiling point organic solvent Oil-2 0.1g 10th layer: Medium-speed green sensitive emulsion layer Emulsion 6 Silver amount 0. Three g Emulsion 7 Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd- E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion 8 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B 0 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil -1 0.02 g High boiling point organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd 0.01 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g Layer 14: Intermediate layer Gelatin 0.6 g Layer 15: Low sensitivity blue sensitive emulsion layer Emulsion 9 Silver amount 0.2 g Emulsion 10 Silver amount 0.3 g Emulsion 11 Silver amount 0.1 g Gelatin 0.8 g Coupler C-50 .2 g Coupler C-6 0.1 g Coupler C-10 0.4 g 16th layer: Medium-speed blue-sensitive emulsion layer Emulsion 11 Silver amount 0.1 g Emulsion 12 Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0. 3 g Coupler C-6 0.1 g Coupler C-10 0.1 g 17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion 13 Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler -6 0.6 g Coupler C-10 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: second protective layer Colloidal silver Ag amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methylmethacrylate and acrylic acid 4: 6 Copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents. The silver iodobromide emulsions 1 to 13 used are as follows.

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Chemical 15]

[0097]

[Chemical 16]

[0098]

[Chemical 17]

[0099]

[Chemical 18]

[0100]

[Chemical 19]

[0101]

[Chemical 20]

[0102]

[Chemical 21]

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

[0105]

[Chemical formula 24]

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

[0108]

[Chemical 27]

[0109]

[Chemical 28]

Then, the emulsion B and the cyan coupler of Sample 101 were replaced with the coupler of the present invention or the comparative coupler (A) as shown in Table 5 to obtain Samples 102 to 11.
6 was produced.

[0111]

[Chemical 29]

Pass the sample through a wedge and
x, 1/50 second exposure. Then, in the first step as shown below, a negative image development was carried out, and a positive image forming treatment was carried out in which color development was carried out using the remaining silver halide. Table 5 shows the relative sensitivities obtained from the exposure amounts required to obtain a cyan color density of 1.0 higher than the minimum density of the image thus obtained. Further, the transmission density of each of the treated samples was measured, a characteristic curve thereof was obtained, and the following performance evaluation was performed. The results are shown in Table 5.

(1) Color developability The logarithm of the exposure amount giving the density of the minimum density (Dmin) +1.0 is found from each characteristic curve, and this is taken as the sensitivity point (S). (ΔS) was calculated. Further, from the sensitivity point S to the high exposure dose side, log = 0.3
The density of the point giving the exposure amount of
The concentration ratio (D%) was calculated with reference to the concentration value of. The results are shown in Table 5. As for ΔS, the higher the positive value, the higher the feeling, and for D, 1
A value greater than 00 represents giving a high color density. (2) Color image fastness The image was stored for 10 days under conditions of 80 ° C. and 70% RH as wet heat fastness. As for light fastness, a xenon fading tester (illuminance: 80,000 lux) was used for exposure for 10 days. After the test, the density of these samples was measured again, and the density after the test at the exposure amount giving the density before test disclosure of 2.0 was calculated as the read color image residual ratio (%).
Shown in. A numerical value closer to 100 indicates that the color image fastness is excellent. The results shown in Table 5 show the following. Sample 1 using the cyan coupler of the present invention with respect to sample 102
In No. 10, although the color-developing color image fastness is improved, the sensitivity is lowered. On the other hand, when the emulsion of the present invention was used, Sample 1
As compared to Sample No. 02, a high sensitization (0.07) is observed as in Sample 101, but color development and color image fastness cannot be improved. Here, in the sample 104 using the emulsion B of the present invention, the sample 110 using the coupler of the present invention was 0.07.
Sensitivity, color development, and color image fastness can all be improved.

[0114]

[Table 5]

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² color development 6 min 38 ° C. 12 liters 2200 ml / m ² adjustment 2 minutes 38 ° C. 4 liters 1100 ml / m ² Bleaching 6 min 38 ° C. 12 liters 220 ml / m ² Fixing 4 min 38 ° C. 8 liters 1100 ml / m ² second Washing with water 4 minutes 38 ° C 8 liters 7500 ml / m ² stability 1 minute 25 ° C 2 liters 1100 ml / m ²

The composition of each processing liquid was as follows. (First developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylene phosphonic acid-5 sodium salt 1.5 g 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide. (Reversal liquid) (Tank liquid) (Replenishing liquid) Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-aminophenol 0 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 The pH was adjusted with hydrochloric acid or sodium hydroxide. (Color developer) (Tank solution) (Replenisher) Nitrilo-N, N, N-trimethylene phosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl- 4-aminoaniline / 3/2 sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH is hydrochloric acid or water. Adjusted with potassium oxide. (Adjusting liquid) (Tank liquid) (Replenishing liquid) Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g 8.0 g Sodium sulfite 12 g 12 g 1-Thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite adduct 30 g 35 g Water was added to 1000 ml 1000 ml pH 6.30 6.10 The pH was adjusted with hydrochloric acid or sodium hydroxide.

(Bleaching Solution) (Tank Solution) (Replenishing Solution) Ethylenediaminetetraacetic acid / disodium salt / dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 H was adjusted with hydrochloric acid or sodium hydroxide. (Fixing solution) (Tank solution) (Replenishing solution) Ammonium thiosulfate 80 g The same sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to the tank solution 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia. (Stabilizing liquid) (Tank liquid) (Replenishing liquid) Benzisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 g 0.3 g Water added 1000 ml 1000 ml pH 7.0 7.0

[0118]

The silver halide photographic light-sensitive material of the present invention is excellent in color developability, color image fastness and color reproducibility, and exhibits excellent sensitivity.

Claims (1)

[Claims] 1. A photographic light-sensitive material having one or more silver halide emulsion layers on a support, the photographic light-sensitive material being at least one of couplers represented by the following general formula (Ia).
A negative internal latent image type silver halide grain containing a seed and chemically sensitized to a depth of less than 0.02 μm from the grain surface in at least one layer of the silver halide emulsion layer. And a silver halide color photographic light-sensitive material. General formula (Ia): (In general formula (Ia), Za is -NH- or -CH.
(R ₃₎ - represents, Zb and Zc each -C
Represents (R ₄ ) = or -N =. R ₁ , R ₂ and R
₃ has a Hammett's substituent constant σ _p value of 0.20.
The above-mentioned electron-withdrawing groups are represented. However, σ of R ₁ and R ₂
The sum of _p- values is 0.65 or more. R ₄ represents a hydrogen atom or a substituent. However, when two R _4's are present in the formula, they may be the same or different. X represents a hydrogen atom or a group which is released by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. In addition, R ₁ , R ₂ , R ₃ , R ₄ or X
The group may become a divalent group and may be bonded to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. )