JPH06175315A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material improved in color image fastness and color development performance by incorporating a specified coupler in a layer for constituting the photosensitive material and a specified compound in a photosensitive emulsion layer. CONSTITUTION:The silver halide color photographic sensitive material contains at least one of the compounds represented by formula III in the photosensitive emulsion layer and at least one of the cyan couplers in the constituent layer. In formulae I-III, Za is-NH-or-C(R13)-; and each of Zb and Zc is -C(R14)= or-N=; each of R11-R13 is an electron-attractive group having-a Hammett's substituent constant sigmapof >=0.20 but the sum of those of R11 and R12 is >=0.65; each of R14 and R21 is H or a substituent; R22 is a substituent; Z2 is a nonmetallic atomic group necessary to form an N-containing hetero ring; each of X1 and X2 is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing main agent; each of R1 and R2 is an aliphatic or aromatic group or the like and the total C number of them is >=12; and n is 1 or 2.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art Recently, in color photographic light-sensitive materials,
In order to meet the needs of users, increase the sensitivity of photosensitive materials,
Higher image quality is being promoted. Among the latter, the improvement of color reproducibility is being developed as a central issue for improving the image quality of color photographic light-sensitive materials together with the improvement of sharpness and the improvement of graininess. On the other hand, the development processing stability of the photosensitive material,
Further improvement in handling and color image fastness is expected, and the demand for improvement is increasing. From this point of view, researches for improving dye-forming couplers have been actively conducted, but it is hard to say that they have been sufficiently improved. Particularly for cyan couplers, phenol-based or naphthol-based couplers have been consistently used, but the dyes produced from these couplers have unnecessary absorption in the blue and green regions, resulting in color reproducibility. It was a big barrier to improvement. In addition, the small molecular extinction coefficient of the cyan dye formed is also disadvantageous for improving the sharpness of the image.

Recently, a new skeletal cyan dye-forming coupler having a nitrogen-containing heterocycle has been actively studied.
Various heterocyclic compounds have been proposed. For example, diphenylimidazole-based couplers described in JP-A-63-226653, JP-A-63-199352, JP-A-63-250649, JP-A-63-250650, and JP-A-63-250650.
4-554, 64-555, JP-A-1-1052.
Nos. 50 and 1-105251 disclose pyrazoloazole couplers. All of these couplers are said to have improved color reproducibility and are characterized by having excellent absorption characteristics of the formed dye. However, the cyan dyes obtained from the above-mentioned couplers have shortcomings of short-wave absorption and inferior fastness to light and heat, and the coupling activity of the coupler itself is small. I had a problem.

On the other hand, JP-A-4-204730 and 3-
The condensed ring pyrrole cyan couplers described in JP-A-226325 and the like are excellent in spectral absorption characteristics and color developability, and it can be said that future development is highly expected. Further, regarding the color image fastness, it is an important issue to improve the color image fastness without impairing the color developability. Even in the condensed ring pyrrole cyan coupler, it has been strongly desired to further improve both color image fastness and color developability.

[0005]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide color photographic light-sensitive material having improved color image fastness and color developability.

[0006]

The object of the present invention is to provide a halogen having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer on a support. A silver halide color photographic light-sensitive material contains at least one cyan dye forming coupler represented by the following general formula (Ia) or (Ib) in at least one layer constituting the light-sensitive material, and the light-sensitive emulsion layer has the following general content. It has been achieved by a silver halide color photographic light-sensitive material characterized by containing at least one compound represented by the formula (S).

[0007]

[Chemical 3]

(In the formulas (Ia) and (Ib), Za is
Represents —NH— or —CH (R ₁₃ ) —, Zb and Zc
Each represents -C (R < ₁₄ >) = or -N =.
R ₁₁ , R ₁₂ and R ₁₃ each represent an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.20 or more. However,
The sum of the σ _p values of R ₁₁ and R ₁₂ is 0.65 or more. R ₁₄
And R ₂₁ each represent a hydrogen atom or a substituent. However, when two R _14's are present in the formula, they may be the same or different. R ₂₂ represents a substituent, and Z ₂ represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. )

[0009]

[Chemical 4]

(In the formula (S), R ₁ and R ₂ are aliphatic groups,
It represents an aryl group or a heterocyclic group, and the total number of carbon atoms of R ₁ and R ₂ is 12 or more. n represents 1 or 2.
However, R ₁ and R ₂ may be the same or different and may be linked to each other to form a ring. )

The cyan couplers represented by (Ia) and (Ib) of the present invention will be described in detail below. In the general formula (Ia), Za is -NH- or -CH.
(R ₁₃ )-, Zb and Zc are each -C (R
₁₄ ) = or -N =. Therefore, the cyan coupler represented by the general formula (Ia) of the present invention is specifically represented by the following general formulas (IIa) to (IXa).

[0012]

[Chemical 5]

(In the general formulas (IIa) to (IXa), R ₁₁ and R
₁₂ , R ₁₃ , R ₁₄ and X ₁ have the same meanings as in formula (Ia). ) In the general formula (Ia), the general formulas (IIa) and (IIIa)
Alternatively, a cyan coupler represented by (IVa) is preferable,
A cyan coupler represented by the general formula (IIIa) is particularly preferable.

Each of R ₁₁ , R ₁₂ and R ₁₃ is an electron-withdrawing group having a σ _p value of 0.20 or more, and the sum of the σ _p values of R ₁₁ and R ₁₂ is 0.65 or more. The sum of the σ _p values of R ₁₁ and R ₁₂ is preferably 0.70 or more, and the upper limit is about 1.8.

Each of R ₁₁ , R ₁₂ and R ₁₃ 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 was established in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
A rule of thumb put forward by LP Hammett, which is widely accepted today. There are σ _p values and σ _m values in the substituent constants obtained by the Hammett's rule, and these values are described in many general textbooks.
JA Dean ed. "Lange's Handbook of Chemistry" 12th
Edition, 1979 (McGraw-Hill) and "Chemistry special issue", 122
Issue, pages 96-103, 1979 (Nankodo). In the present invention, R ₁₁ , R ₁₂ and R ₁₃ are Hammett's substituent constants σ _p
Although it is defined by the value, it does not mean that the values known in the literature described in these publications are limited only to certain substituents, and even if the value is unknown in the literature, when measured based on Hammett's rule, As a matter of course, it is included as long as it is included in the range.

Specific examples of R ₁₁ , R ₁₂ and R ₁₃ , 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 and 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,
Halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with other electron-withdrawing group having a σ _p value of 0.20 or more, heterocyclic group, halogen atom, azo group, or seleno Cyanate group can be mentioned. Among these substituents, the group capable of further having a substituent may further have a substituent as described later for R ₁₄ .

R ₁₁ , R ₁₂ and R ₁₃ will be described in more detail. As the electron-withdrawing group having a σ _p value of 0.20 or more, an acyl group (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 (for example, 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 (Eg, diphenylphosphono), diarylphosphinyl group (eg, diphenylphosphinyl), alkylsulfinyl group (eg, 2-phenoxypropylsulfinyl), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), alkyl A sulfonyl group (for example, methanesulfonyl, octanesulfonyl),
An arylsulfonyl group (eg, benzenesulfonyl,
Toluenesulfonyl), a sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), an acylthio group (eg, acetylthio, benzoylthio), a 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 of another electron-withdrawing group, a heterocyclic group (for example, 2-benzooxa). 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), a trifluoromethanesulfonyl group (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 so on.

Preferred as R ₁₁ , R ₁₂ and R ₁₃ are electron withdrawing groups having a σ _p value of 0.35 or more,
Acyl group, 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, halogenated aryloxy Examples thereof include groups, halogenated aryl groups, aryl groups substituted with two or more nitro groups, and heterocyclic groups. Among them, cyano group, alkoxycarbonyl group,
Aryloxycarbonyl and a halogenated alkyl group are preferable, and a cyano group, an alkoxycarbonyl group which is unsubstituted or substituted by a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, an aryloxycarbonyl group which is unsubstituted or substituted by an alkyl group or an alkoxy group Is more preferable. In the present invention, more preferably R ₁₁ and R
_At least one of ₁₂ and R ₁₃ is an electron-withdrawing group having a σ _p value of 0.60 or more. Examples of the electron-withdrawing group having a σ _p value of 0.60 or more include a nitro group, a cyano group, and an arylsulfonyl group. A cyano group is particularly preferable as R ₁₁ .

R ₁₄ represents a hydrogen atom or a substituent (including an atom), 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 ₁₄ .

More specifically, R ₁₄ 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, 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), aryl groups (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-
Di-tert-amylphenoxyacetamido) phenyl), a heterocyclic group (eg 3-pyridyl, 2-furyl, 2
-Thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy,
4-tert-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), complex Ring oxy groups (eg 2-benzimidazolyloxy, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), alkyl aryl or heterocyclic thio groups (eg methylthio, ethylthio, octylthio, tetradecylthio, 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), a silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (for example, dodecylsulfonyloxy), an acylamino group (for example, acetamide, benzamide, tetradecanamide), 2 -(2,4-di-tert-amylphenoxy) acetamide, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecaneamide, 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) -Tetradecanamido anilino, N-acetylanilino, 2-chloro-5- [α-2-tert-butyl-4-hydroxyphenoxy) dodecanamide] anilino, 2-chloro-5-
Dodecyloxycarbonylanilino), 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-phenylpropanoyl, 4-dodecyloxybenzoyl), alkyl aryl or heterocyclic sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl,
Toluenesulfonyl), a sulfinyl group (for example, octansulfinyl, dodecylsulfinyl, dodecanesulfinyl, phenylsulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), an alkyl aryl or a heterocyclic oxycarbonyl group (for example, methoxycarbonyl, Butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), alkyl aryl or heterocyclic oxycarbonylamino groups (eg methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino, 2 , 4-di-tert-
Butylphenoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butylbenzenesulfonamide), carbamoyl group (For example, N-ethylcarbamoyl, N,
N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-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, sulfo group, unsubstituted amino group and the like.

R ₁₄ 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 or 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.

Examples of the substituents for R ₂₁ and R ₂₂ in the general formula (Ib) include the above-mentioned substituents for R ₁₄ . In formula (Ib), at least one of R ₂₁ and R ₂₂ is preferably an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more, and more preferably σ _p value of 0. The electron withdrawing group is 0.35 or more, more preferably 0.60 or more. Particularly preferably, at least one of R ₂₁ and R ₂₂ is a cyano group. The Hammett's substituent constant σ _p value is as described for R ₁₁ above for each electron-withdrawing group. Z ₂ in the general formula (Ib) represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. The four divalent linking groups for constituting the nitrogen-containing 6-membered heterocycle include -NH
-, -N (R)-, -N =, -CH (R)-, -CH
=, -C (R) =, -CO-, -S-, -SO-, -S
O ₂ − and the like can be mentioned. Here, R represents a substituent, and examples thereof include the substituents mentioned for R ₁₄ . Examples of the dissociative group include those having an acidic proton such as -NH- and -CH (R)-, and preferably the pKa in water is 3 to 12.
With a value of.

The coupler represented by the general formula (Ib) is preferably one represented by the following general formulas (IIb) to (XIXb).

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

(In the general formulas (IIb) to (XIXb), R ₂₁ and R
₂₂ and X ₂ have the same meaning as in general formula (Ib). R ₂₃ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ each represent a hydrogen atom or a substituent, and R ₂₄ represents a substituent. E
WG represents an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.35 or more. ) In the general formula (Ib), the general formulas (IIb) and (IIIb)
Alternatively, the coupler represented by (VIIIb) is preferable. R ₂₃ ,
The substituents for R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are the same as those mentioned for R ₁₄ . As the electron withdrawing group of EWG,
This is as described for R ₁₁ above.

X ₁ and X ₂ are each 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 a “leaving group”).
And the leaving group is a halogen atom, an aromatic azo group, an alkyl group, an aryl group or a heterocyclic group, an alkyl group or an arylsulfonyl group which binds to the coupling position via an oxygen / nitrogen / sulfur or carbon atom. Group, an arylsulfinyl group, an alkyl aryl or a heterocyclic carbonyl group, or a heterocyclic group bonded to a coupling position at a nitrogen atom, and examples thereof include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or arylsulfonyloxy group. Group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl aryl or heterocyclic thio group, carbamoylamino group, arylsulfinyl group,
There is an arylsulfonyl group, a 5-membered or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, etc., and the alkyl group, aryl group or heterocyclic group contained in these leaving groups is a substituent at R _14. It may be further substituted, and when two or more of these substituents are present, they may be the same or different, and these substituents may further have the substituents mentioned for R ₁₄ .

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, tetradecinoyloxy, 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), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (eg, 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 ₁₄ . 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 leaving groups are a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group, and a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. And an arylthio group is particularly preferable.

In the cyan coupler represented by the general formula (Ia) or (Ib), each substituent on the mother nucleus contains a cyan coupler residue represented by the general formula (Ia) or (Ib). It may form a dimer or higher polymer, or may contain a polymer chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound having a cyan coupler residue represented by the general formula (Ia) or (Ib). Is a typical example. In this case, one or more kinds of cyan color-forming repeating units having a cyan coupler residue represented by the general formula (Ia) or (Ib) may be contained in the polymer, and as a copolymerization component, an acrylic acid ester or a methacrylic acid may be used. 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 acid esters and maleic acid esters. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

Substituents used in the above compound examples are as follows.

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

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. Synt
h., I, 270 (1941), J. Chem. Soc., 5149.
(1962), Hetrocyclic., 27, 2301 (19
88), Rec. Trav. Chim., 80, 1075 (196).
It can be synthesized by the method described in 1), the literature cited therein or a similar method.

Next, a specific synthesis example will be shown. (Synthesis Example 1) Synthesis of Exemplified Compound (Ia-9) Exemplified Compound (Ia-9) was synthesized by the following route.

[0055]

[Chemical 29]

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 combined, 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. While 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 (9 cc) was added to a solution of (4a) (7.04 g, 20 mmol) in acetonitrile (30 ml) at room temperature, followed by triphenylphosphine (5.
76 g, 22 mmol) are added and the mixture is heated under 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 silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4:
Purification in 1) gave (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 the residue was purified by column chromatography to obtain 1.6 g of the desired exemplary compound (Ia-9).
The melting point was 97-98 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound (IIIb) -1

[0061]

[Chemical 30]

2-amino-3-cyano-4-phenylpyrrole (compound a) (18.3 g), which is easily obtained by condensing 2-aminoacetophenone hydrochloride and malononitrile in the presence of an alkali, and diethyl ethoxyethylidene malonate (25. Disperse 3 g in 300 ml of ethanol,
Sodium methylate 28%, methanol solution 2
2.0 ml was added and the mixture was heated under reflux for 5 hours. After cooling, ethyl acetate was added, the mixture was washed with water, the organic solvent was concentrated, and the precipitated crystals were collected by filtration to obtain 11.6 g of compound b. Then, 50 ml of Fineoxochol 1600 and Ti
(O-i-Pr) ₄ (2.0 g) was added, and the oil bath temperature was adjusted to 130-
Heated at 140 ° C. for 6 hours. After cooling, the product was purified by silica gel chromatography (hexane / ethyl acetate = 1/1) to obtain coupler (IIIb) -1 (14.7 g) as a pale yellow oil.

The cyan coupler of the present invention has the general formula (I
More preferably, the compound represented by a) is used.
The cyan coupler of the present invention may be used as a mixture of two or more kinds, or may be used in combination with a known cyan coupler. The cyan coupler of the present invention is preferably used in the range of 0.01 millimole to 1 millimole per m ² of the light-sensitive material, and more preferably in the range of 0.1 millimole to 0.5 millimole. The cyan coupler represented by formula (Ia) or (Ib) of the present invention can be used by adding it to both the light-sensitive silver halide emulsion layer and the non-light-sensitive layer. It is preferably added to the emulsion layer.

Next, the compound represented by formula (S) will be described in detail below.

R ₁ and R ₂ represent an aliphatic group which may be substituted, or an aryl group or a heterocyclic group which may be substituted or may be condensed. The term "aliphatic group" as used herein means an aliphatic group which may be linear, branched or cyclic and may be saturated or unsaturated.

The group which may be substituted on the aliphatic group, aryl group or heterocyclic group of R ₁ and R ₂ is preferably an alkyl group (eg, methyl, ethyl, isopropyl, octyl,
Cyclohexyl, allyl, benzyl), aryl groups (eg, phenyl, 4-methylphenyl, 2-methoxyphenyl, 2-naphthyl), heterocyclic groups (eg, 2-pyridyl), halogen atoms (eg, fluorine, chlorine, bromine). ), A nitro group, a cyano group, an alkoxy group (for example, methoxy, butoxy, 2-ethylhexyloxy), an aryloxy group (for example, phenoxy, 4-methylphenoxy, 2-naphthyloxy), an ester group (for example, methoxycarbonyl, Phenoxycarbonyl), an acyl group (for example, acetyl, benzoyl), an acyloxy group (for example, acetyloxy, benzoyloxy), a carbamoyl group (for example, N-methylcapamoyl, N-phenylcarbamoyl, N, N-dioctylcarbamoyl),
An amide group (eg acetamide, benzoylamide),
Sulfinyl group (for example, methylsulfinyl, phenylsulfinyl), sulfonyl group (for example, methanesulfonyl, benzenesulfonyl), more preferably alkyl group, aryl group, alkoxy group, aryloxy group, ester group, acyloxy group, carbamoyl A group, an amide group, a sulfinyl group, and a sulfonyl group.

R ₁ and R ₂ may be the same or different. R ₁
And the total number of carbon atoms of R ₂ is 12 or more, preferably 16 or more. R ₁ and R ₂ may be linked to each other to form a ring, but R ₁ and R ₂ do not include a coupler residue. That is, the compound represented by the general formula (S) is a non-color forming compound.

Specific examples of R ₁ and R ₂ are shown below.

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.

[0073]

[Chemical 34]

[0074]

[Chemical 35]

[0075]

[Chemical 36]

[0076]

[Chemical 37]

[0077]

[Chemical 38]

[0078]

[Chemical Formula 39]

[0079]

[Chemical 40]

[0080]

[Chemical 41]

[0081]

[Chemical 42]

[0082]

[Chemical 43]

[0083]

[Chemical 44]

[0084]

[Chemical formula 45]

[0085]

[Chemical formula 46]

The synthesis examples of the compound of the present invention are shown below.

1. Synthesis of S-51 and S-87

[0088]

[Chemical 47]

86.5 g (0.3 mol) of thiol (1),
47.1 g (0.3 mol) of benzene bromide (2) and 56 g (0.4 mol) of potassium carbonate were added to 100 parts of dimethylacetamide.
It was dissolved in ml and heated with stirring at 100 ° C. for 6 hours. Ethyl acetate and water were added for extraction, the organic phase was washed with water, dried over magnesium sulfate, and then concentrated to give sulfide (3).
Got Yield 108.1 g (98.8%)

108.1 g (0.29) of sulfide (3)
6 mol) was dissolved in 100 ml of acetic acid, a solution of 1 g of sodium tungstate and 0.2 g of sodium hydroxide in 5 ml of water was added, and hydrogen peroxide solution (31%) was added while stirring under ice cooling.
49.4 g (0.45 mol) was added dropwise over 30 minutes. After stirring for another 30 minutes, the mixture was stirred at 50 ° C for 1 hour. Ethyl acetate and water were added for extraction, the organic phase was washed with water, dried over magnesium sulfate, and then concentrated. Silica gel column chromatography (ethyl acetate: hexane = 1:
In step 5), S-51 and S-87 were carefully separated and purified. Yield S-51: 51.0 g (45.2%) S-87: 50.5 g (43.0%) The structure was confirmed by NMR, mass spectrum and elemental analysis.
confirmed.

2. Synthesis examples of compounds S-24 and S-69

[0092]

[Chemical 48]

4-dodecylthiophenol (1) 41.
8 g (0.15 mol) was dissolved in 30 ml of methylene chloride,
20.3 g (0.15 mol) of sulfuryl chloride was added dropwise over 10 minutes. After stirring at room temperature for 1 hour, the mixture was distilled under reduced pressure at room temperature for 1 hour with an aspirator to obtain (2).
Anisole (3) 16.
2 g (0.15 mol) and 50 ml of methylene chloride were added, and the mixture was stirred at room temperature for 24 hours. After distilling off methylene chloride, the residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 10) to obtain sulfide (4). Yield 48.7g (84.4%)

38.5 g (0.1 mol) of sulfide (4)
Was dissolved in 50 ml of acetic acid, and 1 g of sodium tungstate, 0.2 g of sodium hydroxide in 5 ml of water and 15.2 g (0.15 mol) of hydrogen peroxide solution (31%) were added at room temperature, and the mixture was heated to 70 ° C. Heat and stir for 2 hours. Ethyl acetate and water were added for extraction, the organic phase was washed with water, dried over magnesium sulfate and then concentrated. By silica gel column chromatography (ethyl acetate: hexane = 1: 5), S
-24 and S-69 were separated and purified. Yield S-24: 15.6 g (38.9%) S-69: 16.7 g (40.1%) The structures of S-24 and S-69 are NMR, mass spectrum,
Confirmed by elemental analysis.

The compound represented by the general formula (S) of the present invention is added in an amount of 1 g of the coupler added to each of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers or adjacent layers thereof.
0.01 g to 10 g, preferably 0.1 g to 5 g
Is the range.

In the present invention, the compound represented by the general formula (S) may be a single compound or a mixture of two or more kinds. In particular, a sulfone compound and a sulfoxide compound having the same R ₁ and R ₂ of the formula (S) are obtained as a mixture at the time of synthesis, or used in a mixed state for being oxidized from a sulfoxide compound to a sulfone compound during storage. It is realistic to be done.

The light-sensitive material of the present invention may have at least one of a blue-color sensitive layer, a green color-sensitive layer and a red color-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
13438, 59-113440, 61-20037, 61-20038
It may contain a coupler, a DIR compound or the like as described in JP-A No. 1994-242, and may contain a color mixing inhibitor as is commonly used. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have 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. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62
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 described in JP-A-206543. As a specific example, from the side farthest from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
It can be installed in the order of / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62-6
As described in Japanese Patent No. 3936, 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 photosensitivity, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than the middle layer. The photosensitivity is gradually reduced toward the support. An arrangement composed of three layers can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. U.S. Pat.Nos. 4,663,271 and 4,705,744 to improve color reproduction.
No. 4,707,436, JP-A-62-160448, 63-89850
It is preferable to dispose the donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL, described in Japanese Patent Publication No. JP-A-2004-320, adjacent to or adjacent to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. 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
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "I. Emulsion production (Emulsi
on preparation and types) ”, and No. 18716 (1979)
No. 307105 (November 1989), 863-865, p. 648, p. 648.
Page, and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chimie et Physique Photo
graphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Phot
ographic Emulsion Chemistry (Focal Press, 1966)),
Zelikman et al., "Manufacturing and Coating of Photographic Emulsions", published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used in the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40% of the average grain size). %) Is preferable).

In the present invention, it is preferable to use 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 it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 ――――――――――――――――――――――― ―――――― 1. Chemical Sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868 5 Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer 6. Light absorber, pages 25 to 26, page 649, right column, page 873 Filter dye, page 650, left column, ultraviolet absorber 7. Stain prevention Agent page 25 Right column Page 650 Left column Page 872 ~ Right column 8. Dye image stabilizer Page 25 Page 650 Left column Page 872 9. Hardener 26 page 651 Left column 874-875 page 10. Binder page 26 page 651 page Left column, pages 873 to 874 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. Anti-static agent, page 27, 650 Page right column, pages 876-877 14. Matte agent, pages 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-2835
It is preferable to contain the mercapto compound described in No. 51. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, dyes dispersed by the method described in International Publication WO88 / 04794 and Japanese Patent Publication No. 1-502912 or European Patent No. 317,308A, U.S. Patent No. 4,420,555, JP-A 1-259358. It is preferable to include the dyes described in No. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 307105, VII-C.
To the patents listed in G. Examples of yellow couplers include U.S. Pat.
22,620, 4,326,024, 4,401,752, 4,24
8,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, U.S. Patent Nos. 3,973,968, 4,3
Those described in 14,023, 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 73,636 are preferred.
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), Japanese Patent Laid-Open No. 60-33552, Research Disclosure No. 24230.
(June 1984), JP-A-60-43659, 61-72238,
60-35730, 55-118034, 60-185951, U.S. Pat.Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 are particularly preferable.
Known cyan couplers that can be used in combination with the cyan coupler of the present invention include phenol-based and naphthol-based couplers, and U.S. Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, 4,296,200, 2,369,929
Issue 2, Issue 2,801,171, Issue 2,772,162, Issue 2,895,826
Issue, Issue 3,772,002, Issue 3,758,308, Issue 4,334,011
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, and U.S. Patent No. 3,44.
6,622, 4,333,999, 4,775,616, 4,451,
No. 559, No. 4,427,767, No. 4,690,889, No. 4,254,21
Nos. 2, 4,296,199, JP-A 61-42658 and the like are preferable. Furthermore, JP-A-64-553, JP-A-64-554,
The pyrazoloazole-based couplers described in JP-A-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 U.S. Pat. No. 3,451,820.
No., No. 4,080, 211, No. 4,367, 282, No. 4,409, 320
No. 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication) 3,
Those described in No. 234,533 are preferable. Colored couplers to correct unwanted absorption of colored dyes are
Disclosure No.17643, Item VII-G, No.30710
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
Those described in 9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368 are preferable. Also,
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in U.S. Pat.No. 4,774,181, and a dye precursor group capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in RD No. 17643, VII-F and 307105, VII-F.
57-151944, 57-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.No. 4,248,962,
Those described in 4,782,012 are preferable. RD No.11
The bleaching accelerator releasing couplers described in 449, No. 24241, JP-A-61-201247 and the like are effective for shortening the processing time having a bleaching ability, and in particular, the tabular halogenated compound described above. The effect is great when it is added to a light-sensitive material using silver particles. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,1
40, 2,131,188, JP-A-59-157638, 59-170
Those described in No. 840 are preferable. In addition, JP-A-60-10702
No. 9, No. 60-252340, JP-A No. 1-44940, No. 1-45687.
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in No. 8,393 and No. 4,310,618,
DI described in JP-A-60-185950 and JP-A-62-24252
R redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No.
Nos. 173,302A and 313,308A, couplers releasing a dye that recolors after separation, ligand releasing couplers described in U.S. Pat.No. 4,555,477, and leuco dyes described in JP-A-63-75747. Examples thereof include couplers and couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, 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, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (described in JP-A-1-80941. It is preferable to add various antiseptics or antifungal agents such as 4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering (Photogr. S) by A. Green et al.
ci. & Eng.), 19 Certificates, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 90% of the maximum swollen film thickness reached after processing for 15 minutes is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150-
500% is preferable.

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

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit developing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following publications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salt described in JP-A-58-16235; West German Patent No. 966,41
No. 0, No. 2,748,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, 49-59644, 53-94927,
Compounds described in Nos. 54-35727, 55-26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, a fixing solution or a bleach-fixing solution is used for adjusting the pH.
Compounds having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-
It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. JP-A-60 mentioned above
As described in No. 191257, such a transportation means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Volume 64, pp. 248-253 (May 1955)
It can be obtained by the method described in (Month issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method for reducing calcium ion and magnesium ion described in No. 62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used. In the processing of the light-sensitive material of the present invention, the washing water has a pH of 4 to
9, and preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used. In addition, 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. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline-based compounds described in U.S. Pat. Metal salt complex described in JP-A-53-13562
The urethane compounds described in No. 8 can be mentioned. The silver halide color light-sensitive material of the present invention, if necessary,
Various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of accelerating color development. Typical compounds are
56-64339, 57-144547 and 58-115438. Various treatment liquids in the present invention are 10 ℃ ~ 50
Used at ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

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

[0117]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited thereto. (Example 1) Preparation of Sample 101 A multilayer color light-sensitive material having each layer having the following composition was prepared on a cellulose triacetate film support having an undercoating thickness of 127 μm and used 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 High boiling organic solvent Oil-2 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-I 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling point organic solvent Oil-3 0.1 g Dye D -4 0.8 mg

[0120]

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.3 g Emulsion B Silver amount 0.2 g Gelatin 0.8 g Coupler C-1 0.20 g Coupler C-2 0.05 g Coupler C -8 0.05 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.2 g Additive P-1 0.1 g

Fifth layer: Medium speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.25 g Coupler C-2 0.2 g High Boiling point organic solvent Oil-2 0.2 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.7 g Additive P-1 0.1 g High boiling point organic solvent Oil-2 0.2 g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.02 g Compound Cpd-J 5 mg High boiling organic solvent Oil-1 0.02g

[0125]

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 g Coupler C-3 0.1 g Coupler C-6 0.05 g Coupler C-7 0.10 g Coupler C-10 0.10 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-J 10 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-1 0.1 g High boiling point organic solvent Oil-2 0.1 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-3 0.1 g Coupler C-6 0.1 g Coupler C-7 0.1 g Coupler C-10 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-L 0. 05g High boiling organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-3 0.2 g Coupler C-6 0.1 g Coupler C-7 0.1 g Coupler C-10 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-K 5 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil-10 0.02 g High boiling point organic solvent Oil-2 0.02 g

Twelfth layer: intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion 0.05 g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Gelatin 0.8 g Coupler C-4 0.2 g Coupler C-5 0.1 g Coupler C-9 0.4 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.5 g Gelatin 0.9 g Coupler C-4 0.1 g Coupler C-5 0.1 g Coupler C-9 0.6 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion M Silver amount 0.2 g Emulsion N Silver amount 0.2 g Gelatin 1.2 g Coupler C-4 0.1 g Coupler C-5 0.1 g Coupler C-9 0.6 g High boiling point organic solvent Oil-2 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 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g

[0136]

[0137]

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 emulsion used for Sample 101 is shown in Table 1 below.

[0139]

[Table 1] ――――――――――――――――――――――――――――――――――― Equivalent sphere Emulsion name Grain characteristics Average grain size fluctuation Coefficient AgI content (μm) (%) (%) ――――――――――――――――――――――――――――――――――― A Single Dispersed 14-sided grain 0.28 16 4.0 B Monodispersed cubic internal latent image type grain 0.30 10 4.0 C Monodispersed cubic grain 0.38 10 5.0 D Monodispersed tabular grain, 0.55 15 2.0 Average Aspect Ratio 3.0 E Monodisperse Cubic Particles 0.20 17 4.0 F Monodisperse Tetrahedral Particles 0.23 16 4.0 G Monodisperse Cubic Internal Latent Image Particles 0.28 11 4.0 H monodisperse cubic grains 0.32 9 3.5 I monodisperse tabular grains, 0.80 15 2.0 average aspect ratio 5.0 J monodisperse cubic grains 0 30 18 4.0 K Monodisperse tetradecahedral grains 0.45 17 4.0 L Monodisperse tabular grains, 0.55 13 2.0 Average aspect ratio 5.0 M Monodisperse tabular grains, 1.00 15 1 5.5 Average aspect ratio 6.0 N monodisperse tabular grains, 1.20 17 1.5 Average aspect ratio 9.0 ―――――――――――――――――――――― ―――――――――――――

The spectral sensitizations of Emulsions A to N are as shown in Tables 2 and 3 below.

[0141]

[Table 2] ――――――――――――――――――――――――――――――――――― Emulsion name Added sensitizing dye Silver halide 1 Addition amount per mole (g) ――――――――――――――――――――――――――――――――――― ASE-2 0.025 SE-3 0.25 SE-8 0.01 B SE-1 0.01 SE-3 0.25 SE-8 0.01 C SE-1 0.01 SE-2 0.01 SE-3 0.25 SE-8 0.01 D SE-2 0.01 SE-3 0.10 SE-8 0.01 E SE-4 0.5 SE-5 0.1 F SE-4 0.3 SE-5 0. 1 G SE-4 0.25 SE-5 0.08 SE-9 0.05 H SE-4 0.2 SE-5 0.06 SE-9 0.05 ――――――――――― ―――――――――― -------------

[0142]

[Table 3] ――――――――――――――――――――――――――――――――――― Emulsion name Added sensitizing dye Silver halide 1 Addition amount per mole (g) ――――――――――――――――――――――――――――――――――― ISE-4 0.3 SE-5 0.07 SE-9 0.1 J SE-6 0.05 SE-7 0.2 K SE-6 0.05 SE-7 0.2 L SE-6 0.06 SE-7 0. 22 M SE-6 0.4 SE-7 0.15 N SE-6 0.06 SE-7 0.22 ――――――――――――――――――――――― ――――――――――――

[0143]

[Chemical 49]

[0144]

[Chemical 50]

[0145]

[Chemical 51]

[0146]

[Chemical 52]

[0147]

[Chemical 53]

[0148]

[Chemical 54]

[0149]

[Chemical 55]

[0150]

[Chemical 56]

[0151]

[Chemical 57]

[0152]

[Chemical 58]

[0153]

[Chemical 59]

[0154]

[Chemical 60]

[0155]

[Chemical formula 61]

[0156]

[Chemical formula 62]

[0157]

[Chemical formula 63]

(Production of Samples 102 to 120) Sample 101
In, the high boiling point organic solvent Oil-2 of the fourth to sixth layers
Cyan couplers C-1 and C- of the fourth layer to the sixth layer were added by substituting the additives shown in Table 4 with equal weight.
Instead of 2, an equimolar amount to the cyan coupler shown in Table 4 (equal to the total number of moles of cyan couplers C-1 and C-2)
Samples 102 to 120 were prepared in the same manner as Sample 101, except that the sample was replaced with and added.

The samples 101 to 120 thus produced were cut into strips and subjected to gradation exposure with an optical wedge,
It processed by the processing process shown below. Evaluation of color development is
The density of the obtained sample was measured to obtain the maximum color density (Dmax) of the cyan image. The light fastness was evaluated by irradiating the sample after measurement with a xenon fading tester (about 100,000 lux) for 8 days from the base direction, and then measuring the density again, and the cyan color developing dye at a cyan image initial density of 2.0. The remaining concentration (%) was shown. The above results are shown together in Table 5.

[0160]

[Table 4]

[0161]

[Table 5]

From Table 5, in the conventional phenol type cyan couplers C-1 and C-2, when the additive of the present invention was used,
The effect was small in both the color-forming property and the light fastness. However, when the cyan coupler of the present invention is used in combination with the additive of the present invention, excellent results can be obtained in which both the color developability and the light fastness are improved. European Patent Nos. 509,311 and 510,576 disclose compounds having a structure similar to that of the additive of the present invention, but there is no specific description about magenta couplers and cyan couplers. The combination of high color development and improvement of light fastness obtained by the combination of the compounds of the present invention is an unpredictable and excellent result.

The processing steps are as follows. Processing process time Temperature 1st development 6 minutes 38 ℃ Washing with water 2 minutes 38 ℃ Reversing 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjusting 2 minutes 38 ℃ Bleaching 6 minutes 38 ℃ Fixing 4 minutes 38 ℃ Washing 4 Min 38 ℃ stable 1 min 25 ℃

The composition of each treatment liquid was as follows.

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

Example 2 Preparation of Sample 201 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were provided. Was applied to prepare a multilayer color photographic paper (Sample 201) having the following layer structure. The coating liquid was prepared as follows.

Preparation of Fifth Layer Coating Solution 33 g of cyan coupler (Ex-C), ultraviolet absorber (U
V-2) 10 g, color image stabilizer (Cpd-9) 0.6 g,
Color image stabilizer (Cpd-10) 0.6 g, color image stabilizer (C
0.6 g, a color image stabilizer (Cpd-8) 0.
6 g, color image stabilizer (Cpd-6) 0.6 g, color image stabilizer (Cpd-1) 18 g, high boiling organic solvent (Solv-
3) Add 33 cc of ethyl acetate to 57 ml to dissolve, and add this solution to 270 cc of 20% gelatin aqueous solution containing 7.0 g of sodium dodecylbenzenesulfonate, and then emulsify and disperse with a high-speed stirrer to prepare an emulsified dispersion. did. On the other hand, silver chlorobromide emulsion (cube, average grain size 0.50μ
m large size emulsion C and 0.41 μm small size emulsion C 1: 4 mixture (silver molar ratio). The variation coefficients of the grain size distribution are 0.09 and 0.11, respectively, and in each size emulsion, 0.8 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. Consisting of). In this emulsion, the red-sensitizing dye E shown below was 0.9 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 1.1 x 10 ^-4 for small size emulsions
Mol is added. Further, Compound F shown below was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

Coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-
The s-triazine sodium salt was used. Also, C for each layer
The total amount of pd-14 and Cpd-15 is 25.0 mg each.
/ M ² and 50.0 mg / m ² were added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0174]

[Table 6]

[0175]

[Table 7]

[0176]

[Table 8]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) is used.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

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

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A having a grain size of 0.70 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd) -3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-6) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having average grain size 0.55 μm and small size emulsion B having 0.39 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd) -6) 0.01 Color Image Stabilizer (Cpd-7) 0.01 Color Image Stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent ( Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-6) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide is locally contained in a part of the grain surface, and the rest is silver chloride. 0.09 Gelatin 0.85 Cyan coupler (Ex-C) 0.33 Ultraviolet absorber (UV-2) 0.1 Color image stabilizer (Cpd-9) 0.006 Color image stabilizer ( Cpd-10) 0.006 color image stabilizer (Cpd-11) 0.006 solvent (Solv-3) 0.66 color image stabilizer (Cpd-8) 0.006 color image stabilizer (Cpd-6) 0 0.006 color image stabilizer (Cpd-1) 0.18

Sixth layer (UV absorbing layer) Gelatin 0.85 UV absorbing agent (UV-1) 0.65 Color image stabilizer (Cpd-12) 0.15 Color image stabilizer (Cpd-5) 0.02

[0186]

[0187]

[Chemical 64]

[0188]

[Chemical 65]

[0189]

[Chemical formula 66]

[0190]

[Chemical formula 67]

[0191]

[Chemical 68]

[0192]

[Chemical 69]

[0193]

[Chemical 70]

[0194]

[Chemical 71]

In order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to each emulsion layer.

[0196]

[Chemical 72]

First, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was applied to each sample.
Was used to give a gray scale exposure of a red filter for sensitometry. The exposure at this time is 25 with the exposure time of 0.1 seconds.
The exposure amount was 0 CMS. The exposed sample was subjected to continuous processing (running test) using a paper processor using a solution having the following process and processing solution composition until the tank was replenished to twice the tank capacity for color development.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161 ml 1 liter Bleach fixing 35 ℃ 45 seconds 215 ml 1 liter Stability (1) 35 ℃ 20 seconds ―― 0.6 liter Stability (2) 35 ℃ 20 seconds ―― 0.6 liter stability (3) 35 ℃ 20 seconds ―― 0.6 liter stability (4) 35 ℃ 20 seconds 248 ml 0.6 liter Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ² of photosensitive material * Stability is a 4-tank countercurrent system from (4) to (1)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 0.8 ml 0.8 ml Lithium sulfate (anhydrous) 2.7 g 2.7 g Triethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g-Potassium bromide 0.03 g 0.025 g Diethylhydroxyamine 4.6 g 7.2 g Potassium carbonate 27 g 27 g Sodium sulfite 0.1 g 0.2 g N-Ethyl-N- (β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 4.5 g 7.3 g Optical brightener (4,4'-diaminostilbene type) 2.0 g 3.0 g Water was added to 1000 ml 1000 ml pH (water Add potassium oxide) 10.25 10.80

[Bleach-fixing solution] (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Glacial acetic acid 9 g Add water to 1000 ml pH (25 ℃) 5.40

[Stabilizer] (tank solution and replenisher are the same) Benzisothiazolin-3-one 0.02 g Polyvinylpyrrolidone 0.05 g Water was added to 1000 ml pH (25 ° C) 7.40

The high boiling point organic solvent So of the fifth layer of the sample 201
50% by weight of the added amount of lv-3 is the additive S-2 of the present invention.
A sample 202 was prepared in the same manner as the sample 201 except that the same weight was replaced with. When Samples 201 and 202 were evaluated according to Example 1, a cyan image excellent in both light fastness and color developability was obtained with Sample 202 of the present invention as in Example 1. However, the light irradiation in the evaluation of light fastness was carried out for 20 days from the emulsion surface direction.

Example 3 Fifth Example 201 Sample 201
50% by weight of the amount of the high boiling point organic solvent Solv-3 added to the layer
A sample 203 was prepared in the same manner as the sample 201 except that the additive S-103 of the present invention was replaced by an equal weight. Sample 2
When 03 was evaluated according to Example 2, the same excellent result was obtained.

(Example 4) Fifth of sample 201 of Example 2
50% by weight of the amount of the high boiling point organic solvent Solv-3 added to the layer
A sample 204 was prepared in the same manner as the sample 201, except that the additive S-24 of the present invention was replaced by an equal weight. Sample 20
4 was evaluated according to Example 2, and similar excellent results were obtained.

(Example 5) Fifth of sample 201 of Example 2
50% by weight of the amount of the high boiling point organic solvent Solv-3 added to the layer
A sample 205 was prepared in the same manner as the sample 201 except that the additive S-84 of the present invention was replaced by the same weight. Sample 20
When 5 was evaluated according to Example 2, the same excellent result was obtained.

Example 6 Fifth Example 202 Sample 202
Sample 206 was prepared in the same manner as Sample 202, except that the coupler Ia-22 of the present invention was replaced by an equimolar amount instead of the cyan coupler Ex-C in the layer. Sample 206 as Example 2
The same excellent results were obtained.

Example 7 Sample No. 5 of Example 2 No. 5
Sample 207 was prepared in the same manner as Sample 202 except that the coupler IIb-2 of the present invention was replaced by an equimolar amount in place of the cyan coupler Ex-C in the layer. When the sample 207 was evaluated according to Example 2, the same excellent result was obtained.

(Example 8) Instead of the cyan couplers Cp-C and Cp-B of the third to fourth layers of the sample 201 of Example 2 described in JP-A-2-90151, the coupler Ia of the present invention was used. -18 is replaced with an equimolar amount based on the total number of moles of the added amount of the same layer, and the additive H of the third to fourth layers
Sample A was prepared in the same manner as Sample 201 except that BS-2 was replaced with the additive S-11 of the present invention in an equal weight. After the sample A was treated by the method described in the above publication and evaluated in accordance with Example 1 of the present specification, the same excellent result was obtained.

Example 9 Third Layer of Sample A of Example 8
The additive S- of the present invention instead of the additive S-11 of the fourth layer
A sample B was prepared in the same manner as the sample A except that 84 was replaced with the same weight. When the sample B was evaluated according to Example 8, the same excellent result was obtained.

[0210]

According to the present invention, a silver halide color photographic light-sensitive material excellent in both light fastness and color developability of a cyan image can be obtained.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and at least one layer each on a support.
And a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, at least one of cyan dye forming couplers represented by the following general formula (Ia) or (Ib) is contained in at least one layer constituting the light-sensitive material. And a silver halide color photographic light-sensitive material characterized in that the light-sensitive emulsion layer contains at least one compound represented by the following general formula (S). [Chemical 1] (In the formula (Ia) and (Ib), Za is -NH- or -CH (R ₁₃₎ - and represents, Zb and Zc each -C (R ₁₄₎ = or represent -N = .R ₁₁ , R ₁₂ and R
₁₃ has a Hammett's substituent constant σ _p value of 0.20.
The above-mentioned electron-withdrawing groups are represented. However, σ _{p of} R ₁₁ and R ₁₂
The sum of the values is 0.65 or more. R ₁₄ and R ₂₁ each represent a hydrogen atom or a substituent. However, when two R _14's are present in the formula, they may be the same or different. R ₂₂ represents a substituent, and Z ₂
Represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered heterocycle. However, the heterocycle has at least one dissociative group. X ₁ and X ₂ each represent a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. ) [Chemical 2] (In the formula (S), R ₁ and R ₂ represent an aliphatic group, an aryl group or a heterocyclic group, and the total number of carbon atoms of R ₁ and R ₂ is 12 or more. N represents 1 or 2 However, R ₁ and R ₂ may be the same or different and may be linked to each other to form a ring.)