JPH05297536A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and color reproduction performance and to reduce variation of photographic performance with the lapse of time from manufacture to photographing. CONSTITUTION:The silver halide color photographic sensitive material has at least one photosensitive silver halide emulsion layer containing a cyan coupler and a yellow-colored cyan coupler represented by formula I and II which Za is -NH- or -CH(R13)-; each of Rb and Rc is -C(R14)= or -N=; each of R11-R13 is an electron-attractive group having a Hammett's substituent constant sigmap of >=0.20 and the sum of sigmap of both is >=0.65; each of R14 and R21 is H or a substituent; R22 is a substituent; Z2 is a a nonmetallic atomic group necessary to form an N-containing 6-membered hetero ring; and 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 agent.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art The exposed aromatic silver halide as an oxidant reacts with the oxidized aromatic primary amine type color developing agent and the coupler to give indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine. It is well known that a color image is formed by forming a dye and a dye similar thereto. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta and cyan dyes. Of these, phenol or naphthol couplers are commonly used to form cyan dye images. However, since these couplers have an unfavorable absorption in the green region, they have a serious problem of significantly reducing color reproducibility, and it is desired to solve these problems. Japanese Patent Laid-Open No. 63-141
The coupler proposed in No. 057 is excellent as a magenta coupler in terms of color image storability, but further improvement is desired for use as a cyan coupler. Further, for the purpose of improving the hue of a cyan color image and improving the color reproducibility, a pyrrolopyrazole type coupler is proposed in EP-0456226A1. Although these couplers are excellent in color developability, the color image storability is improved, and the hue of the color forming dye is considerably improved, their use causes a problem in color reproducibility and a decrease in sensitivity. I also had the problem.

On the other hand, a silver halide color photographic light-sensitive material capable of improving color reproducibility by using a yellow color docyan coupler has been disclosed in JP-A-1-319744 and JP-A-3-19744.
No. 177836, No. 3-177837, and European Patent No. 423,727A have been proposed, but further improvement in color reproducibility has been desired. Further, these photosensitive materials have problems that they have a long aging period and that their photographic performance changes when exposed to high temperature and high humidity conditions.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is, firstly, to provide a light-sensitive material having high sensitivity and excellent color reproducibility, and secondly, from manufacturing to photographing. It is an object of the present invention to provide a light-sensitive material having little change in photographic performance over time.

[0005]

The above objects have been achieved by the following method. In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the following general formula (1-a) or (1-b)
A silver halide color photographic light-sensitive material containing a cyan coupler represented by and a yellow colored cyan coupler.

[0006]

[Chemical 2]

(In the formula, Za is --NH-- or --CH (R
₁₃ )-, and Zb and Zc are each -C.
Represents (R ₁₄ ) = or -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 of R ₁₁ and R ₁₂
The sum of p 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, Z
₂ represents a non-metal atomic 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. )

The cyan coupler of the present invention will be described in detail below. In the general formula (Ia), Za is -NH-.
Or -CH (R ₁₃₎ - represents, Zb and Zc each -C (R ₁₄₎ = or represent -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).

[0009]

[Chemical 3]

(Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and X ₁
Are synonymous with each in the general formula (Ia). )
In the general formula (Ia), the general formulas (IIa) and (IIIa)
Alternatively, a cyan coupler represented by the formula (IVa) is preferable, and a cyan coupler represented by the general formula (IIIa) is particularly preferable.

R ₁₁ , R ₁₂ and R ₁₃ are all electron withdrawing groups of 0.20 or more, and the sum of σ p values of R ₁₁ and R ₁₂ is 0.65 or more. The sum of σ p values of R ₁₁ and R ₁₂ is preferably 0.70 or more, and the upper limit is 1.
It is about 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 σp value of 0.35 or more is preferable, and an electron withdrawing group having a σp value of 0.60 or more is more preferable. The upper limit is an electron-withdrawing group of 1.0 or less. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
L. in the year P. A rule of thumb put forward by Hammett, which is widely accepted today. Substituent constants determined by Hammett's law include σ p values and σ m values, and these values are described in many general textbooks. A. Dean's `` Lange's Handbook of Ch
"emistry", 12th Edition, 1979 (Mc Graw-Hill) and "Special Issue on Chemistry", 122, 96-103, 19
Detailed in 1979 (Nankodo). In the present invention, R ₁₁ and R ₁₂
And R ₁₃ are defined by the Hammett's substituent constant σ p value, but this does not mean that the values known in the literatures described in these publications are limited to certain substituents, and that value is unknown in the literature. Needless to say, it is included as long as it falls within the range when measured based on the Hammett's rule.

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 acyl group, acyloxy group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group and 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, thiocarbonyl Group, halogenated alkyl group, halogenated alkoxy group,
A halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp of 0.20 or more, a heterocyclic group,
Examples thereof include a halogen atom, an azo group and a selenocyanate group. Among these substituents, the group capable of further having a substituent may further have a substituent as described later for R ₁₄ .

R ₁₁ , R ₁₂ and R ₁₃ will be described in more detail. Examples of the electron withdrawing group having a σ p value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyl). Oxybenzoyl), acyloxy group (eg acetoxy), carbamoyl group (eg carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamide) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, 2-
Decyl-hexyloxycarbonylmethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl, 2,5-amylphenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (For example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl), alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), arylsulfinyl group (for example, 3-pentadecylphenylsulfinyl), alkyl A sulfonyl group (for example, methanesulfonyl, octanesulfonyl),
An arylsulfonyl group (eg, benzenesulfonyl,
Toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio group (eg, acetylthio, benzoylthio), sulfamoyl group (eg, N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (for example,
Methylthiocarbonyl, phenylthiocarbonyl), halogenated alkyl groups (eg trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg trifluoromethyloxy), halogenated aryloxy groups (eg pentafluorophenyloxy), halogens Alkylamino group (for example, N, N-di- (trifluoromethyl) amino), halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2-tetrafluoroethylthio), σp value is 0 An aryl group (for example, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) substituted with 20 or more other electron-withdrawing groups, a heterocyclic group (for example, 2-benzoxazoli) 2-benzothiazolyl, 1-phenyl-2-
Benzimidazolyl, 5-chloro-1-tetrazolyl,
1-pyrrolyl), a halogen atom (eg chlorine atom, bromine atom), an azo group (eg phenylazo) or a selenocyanate group.

Typical σ p values of electron withdrawing groups are cyano group (0.66), nitro group (0.78), trifluoromethyl group (0.54), acetyl group (0.5
0), trifluoromethanesulfonyl (0.92), methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred as R 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 with a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, an aryloxycarbonyl group which is unsubstituted or substituted with 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 σp 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 as the substituent, 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, and more specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-Pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), 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-
tert-amylphenoxyacetamido) phenyl), a heterocyclic group (for example, 3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group (for example, methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy,
2-methanesulfonylethoxy), an aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-te
rt-Butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), heterocyclic oxy A group (for example, 2-benzimidazolyloxy, 1-phenyltetrazole-5-oxy,
2-tetrahydropyranyloxy), an alkyl aryl or a heterocyclic thio group (for example, 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, tetradecane amide), 2 -(2,4-tert-amylphenoxyacetamide, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy)] decanamide, isopentadecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide, 4 -(3-t-butyl-4-hydroxyphenoxy) butanamide), alkylamino group (for example, methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, methylbutylamino), aryla A mino group (eg, phenylamino,
2-chloroanilino, 2-chloro-5-tetradecanamidoanilino, N-acetylanilino, 2-chloro-5
-[Α-2-tert-butyl-4-hydroxyphenoxy) dodecanamide] anilino, 2-chloro-5-dodecyloxycarbonylanilino), ureido group (for example, methylureido, phenylureido, N, N-dibutylureido) , Dimethylureido), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), an alkenyloxy group (for example, 2-propenyloxy), a formyl group, Alkyl-aryl or heterocyclic acyl groups (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, 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 formula (Ib) include the substituents for R ₁₄ described above. 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 0.35. The electron withdrawing group of at least 0.60 is more preferable. Particularly preferably, at least one of R ₂₁ and R ₂₂ is a cyano group. The Hammett's substituent constant σ p values are 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. (R represents a substituent,
_The substituents listed in ₁₄ can be mentioned. ) As a dissociative group, −
Examples thereof include those having an acidic proton such as NH- and -CH (R)-, and those having a pKa value in water of 3 to 12 are preferable.

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

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

(In the formula, R ₂₁ , R ₂₂ and X ₂ have the same meanings as in 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. EXG 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 (III
A coupler represented by b) or (VIIIb) is preferred. 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 EXG,
This is as described for R ₁₁ above.

X ₁ and X ₂ each represent a hydrogen atom or a group which leaves when the coupler reacts with an oxidized product of an aromatic primary amine color developing agent (hereinafter, simply referred to as “leaving group”). The leaving group is a halogen atom, an aromatic azo group, an alkyl group, an aryl group or a heterocyclic group, an alkyl or arylsulfonyl group, an arylsulfinyl group, which couples a coupling position via an oxygen / nitrogen / sulfur or carbon atom. , An alkyl / aryl or a heterocyclic carbonyl group or a heterocyclic group bonded to the coupling position at a nitrogen atom, for example, a halogen atom,
An alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an acylamino group, an alkyl or aryl sulfonamide group,
Alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl / aryl or heterocyclic thio group, carbamoylamino group, arylsulfonyl group, arylsulfonyl group, 5- or 6-membered nitrogen-containing heterocyclic group, imide group, arylazo group, etc. And the alkyl group, aryl group, or heterocyclic group contained in these leaving groups may be further substituted with the substituent for R ₁₄ , and when these substituents are two or more, they may be the same or different. Or 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, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino (E.g., di-chloroacetyl amino, heptafluorobutyryl amino), alkyl or aryl sulfonamido group (e.g., methanesulfonic amino, trifluoromethanesulfonic amino, p
-Toluenesulfonylamino), an alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (for example, phenoxycarbonyloxy),
Alkyl-aryl or heterocyclic thio groups (eg,
Ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), arylsulfonyl group (for example, 2-butoxy-5-tert-octylphenylsulfonyl), arylsulfinyl group (for example, 2-butoxy-5-tert-
Octylphenylsulfinyl), a carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2- Dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. Of course, these groups may be further substituted with the groups listed as the substituent for R 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.

The cyan coupler represented by the general formula (Ia) or (Ib) contains a cyan coupler residue in which each substituent on the mother nucleus is represented by the general formula (Ia) or (Ib). 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 an addition polymer having a cyan coupler residue represented by the general formula (Ia) or (Ib), a homopolymer or copolymer of an ethylenically unsaturated compound. 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.

[0029]

[Chemical 7]

[0030]

[Chemical 8]

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Chemical 11]

[0034]

[Chemical 12]

[0035]

[Chemical 13]

[0036]

[Chemical 14]

[0037]

[Chemical 15]

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

Substituents used in the above compound examples are as follows.

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

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.Am.Chem., 81
No., 2452 (1959), J. Am. Chem. Soc., 112, 2465 (1990), Or.
g.Synth., I 270 (1941), J.Chem.Soc., 5149 (1962), Hetr
ocyclic., 27, 2301 (1988), Rec.Trav.chim., 80,1075
It can be synthesized by the method described in (1961) and the like, 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.

[0052]

[Chemical 28]

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

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

Carbon tetrachloride (9c) was added to a solution of (4a) (7.04g, 20mmol) in acetonitrile (30ml) at room temperature.
c) is added, followed by triphenylphosphine (5.76).
g, 22 mmol) and 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 the residue was purified by silica gel column chromatography (developing solvent, hexane: ethyl acetate = 4: 1) to obtain (5a) (1.13 g, 17%). The obtained 1.8 g of (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane, and 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). Melting point is 97-98 ° C
Met. (Synthesis Example 2) Synthesis of Exemplified Compound (IIIb) -1

[0056]

[Chemical 29]

2-amino-3-cyano-4-phenylprolol (Compound a) (18.3 g) 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. Next, fine oxochol 1600 50 ml, Ti (Oi-Pr)
₄ 2.0 g was added and heated at an oil bath temperature of 130-140 ° C. for 6 hours. After cooling, the residue was purified by silica gel chromatography (hexane / ethyl acetate = 1/1) to obtain 14.7 g of coupler (IIIb) -1 as a pale yellow oily substance.

Next, the yellow-colored cyan coupler of the present invention will be described.

In the present invention, a yellow colored cyan coupler has a maximum absorption in the visible absorption region of the coupler between 400 nm and 500 nm and is coupled with an oxidized product of an aromatic primary amine developing agent to form a visible absorption. It is a cyan coupler that forms a cyan dye having an absorption maximum in the region of 630 nm to 750 nm.

Among the yellow colored cyan couplers of the present invention, a water-soluble 6-hydroxy-2-pyridone-5-ylazo group and a water-soluble pyrazolone are formed by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. A cyan coupler capable of releasing a compound residue containing a 4-ylazo group, a water-soluble 2-acylaminophenylazo group or a water-soluble 2-sulfonamidophenylazo group is preferably used.

The colored cyan coupler of the present invention is preferably represented by (CI) to (CIV) shown in the following general formula 30.

[0062]

[Chemical 30]

In the general formulas (CI) to (CIV), Cp
Is a cyan coupler residue (T is attached to its coupling position), T is a timing group, k is an integer of 0 or 1 and X includes N, O, or S (T) _It represents a divalent linking group which binds to _k and links Q, and Q represents an arylene group or a divalent heterocyclic group.

In the general formula (CI), R ₁₁ and R ₁₂ are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group,
An alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamide group or an alkylsulfonyl group, and R ₁₃ is a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group or a heterocyclic group, respectively. However, at least one of T, X, Q, R ₁₁ , R ₁₂ or R ₁₃ contains a water-soluble group (for example, hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxysulfonyloxy).

The group represented by the following chemical formula 31 in the general formula (CI)

[0066]

[Chemical 31]

It is common knowledge that can have the following tautomeric structures, and these tautomeric structures are also included in the structure defined by the general formula (CI) of the present invention.

[0068]

[Chemical 32]

In the general formula (CII), R ₁₄ represents an acyl group or a sulfonyl group, R ₁₅ represents a substitutable group, and j represents an integer of 0 to 4. When j is an integer of 2 or more, R ₁₅ may be the same or different. However, T, X,
At least one of Q, R ₁₄ or R ₁₅ is assumed to contain a water-soluble group (eg, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniumyl).

In the general formulas (CIII) and (CIV), R ₁₆
Is a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic group, an alvamoyl group, a sulfamoyl group, a carbonamido group, a sulfone. An amide group or an alkylsulfonyl group, and R ₁₇ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, at least one of T, X, Q, R ₁₆ or R ₁₇ contains a water-soluble group (for example, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniumyl).

Further, the group represented by the following chemical formula 33:

[0072]

[Chemical 33]

Are the same compounds in a tautomeric relationship.

The compounds represented by formulas (CI) to (CIV) will be described in more detail below.

Examples of the coupler residue represented by Cp include known cyan coupler residues (for example, phenol type and naphthol type).

The timing group represented by T is represented by the general formula (C
I) to (CIV) is a group in which the bond with Cp is cleaved after the bond with Cp is cleaved by a coupling reaction between the coupler represented by I) to (CIV) and the oxidized product of the aromatic primary amine developing agent,
It is used for various purposes such as adjustment of coupling reactivity, stabilization of coupler, adjustment of release timing of X and below. Examples of the timing group include known linking groups represented by the following Chemical Formula 34. In each group shown in Chemical formula 34, the * mark is bonded to Cp, and the ** mark is bonded to X.

[0077]

[Chemical 34]

In the formula, R ₂₀ represents a group capable of substituting on the benzene ring, R ₂₁ represents R ₄₁ described below, and R ₂₂ represents a hydrogen atom or a substituent. t represents an integer of 0 to 4. The substituents of R ₂₀ and R ₂₂ include R ₄₁ , a halogen atom, R ₄₃ O—, R ₄₃ S—, R ₄₃ (R ₄₄ ) NCO—, R
₄₃ OOC−, R ₄₃ SO ₂ −, R ₄₃ (R ₄₄ ) NSO ₂ −,
R ₄₃ CON (R ₄₃ ) −, R ₄₁ SO ₂ N (R ₄₃ ) −, R ₄₃
CO-, R ₄₁ COO-, R ₄₁ SO-, nitro, R ₄₃ (R
₄₄ ) NCON (R ₄₅ )-, cyano, R ₄₁ OCON
_{(R 43) -, R 43} OSO 2 -, R 43 (R 44) N-, R 43
(R ₄₄ ) NSO ₂ N (R ₄₅ ) —, or a group represented by the following chemical formula 35:

[0079]

[Chemical 35]

Examples include:

In the above formula, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom or an aliphatic group. Represents a group, an aromatic group or a heterocyclic group.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group. Representative examples are methyl, ethyl, propyl, isopropyl, butyl, (t) butyl,
(I) Butyl, (t) amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-
Mention may be made of tetramethylbutyl, decyl, dodecyl, hexadecyl or octadecyl.

The aromatic group is a phenyl group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted naphthyl group.

The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, and is selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and is preferably a substituted or unsubstituted 3- to 8-membered ring. It is a heterocyclic group. As typical examples of the heterocyclic group, 2-pyridine, 2-thienyl, 2-furyl, 1,3,4-thiadiazol-2-yl, 2,4-
Dioxo-1,3-imidazolidin-5-yl, 1,
2,4-triazol-2-yl or 1-pyrazolyl may be mentioned.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents are:
Halogen atom, R ₄₇ O-, R ₄₆ S-, R ₄₇ CON
_{(R 48) -, (R} 47) (R 48) NCO-, R 46 OCON
_{(R 47) -, R 46} SO 2 N (R 47) -, (R 47)
_{(R 48) NSO 2 -,} R 46 SO 2 -, R 47 OCO-,
(R ₄₇ ) (R ₄₈ ) NCON (R ₄₉ ) —, a group having the same meaning as R ₄₆ , a group represented by the following chemical formula 36,

[0086]

[Chemical 36]

R ₄₆ COO—, R ₄₇ OSO ₂ —, a cyano group or a nitro group can be mentioned. Where R ₄₆ is an aliphatic group,
It represents an aromatic group or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of an aliphatic group, an aromatic group or a heterocyclic group has the same meaning as previously defined.

K is an integer of 0 or 1, but it is generally preferred that k is 0, that is, Cp and X are directly bonded.

X is a divalent linking group which is bonded to (T) _k or more by N, O or S, and is --O--, --S--, --OC.
O-, -OCO (O)-, -OCO (S)-, -OCO
_{NH -, - SO 2 -,} - Hajime Tamaki binds to OSO ₂ NH- or N with (T) _k or (e.g. pyrrolidine,
Piperidine, morpholine, piperazine, pyrrole, pyrazole, imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,
4-dione, a group derived from 1,2,4-triazolidine-3,5-dione) or these groups and an alkylene group (for example, methylene, ethylene, propylene), a cycloalkylene group (for example, 1,4-cyclohexylene) ), An arylene group (eg, o-phenylene, p-phenylene), a divalent heterocyclic group (eg, a group derived from pyridine, thiophene, etc.), —CO—, —SO ₂ —, —CO.
O -, - CONH -, - SO 2 NH -, - SO 2 O-,
_{-NHCO -, - NHSO 2 -,} - NHCONH -, -
A linking group formed by combining NHSO ₂ NH-, -NHCOO- and the like is preferable. X is more preferably represented by the general formula (I).

General formula (I) * -X _1- (L-X ₂ ) _m -** In the general formula (I), * is a position to be bonded to (T) _k or more, and ** is a position to be bonded to Q or less. Position, X ₁ is —O— or —S—, L is an alkylene group, and X ₂ is —O—, —S.
-, - CO -, - SO 2 -, - OCO -, - COO-,
-NHCO -, - CONH -, - SO 2 NH -, - NH
_{SO 2 -, - SO 2 O} -, - OSO 2 -, - OCO
(O)-, -OCONH-, -NHCOO-, -NHC
_{ONH -, - NHSO 2 NH -} , - OCO (S) -, -
SCO (O) -, - OSO 2 NH- or -NHSO ₂
O- and m represent an integer of 0 to 3. The total number of carbon atoms of X (hereinafter referred to as C number) is preferably 0 to 12, and more preferably 0 to 8. Most preferred as X is -OC.
H ₂ CH ₂ is O-.

Q represents an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may have a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino,
Ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamide, sulfonamide, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl), and the C number is preferably 6 to 15 , And more preferably 6 to 10. When Q is a divalent heterocyclic group,
The heterocyclic group is a 3- to 8-membered ring containing at least one hetero atom selected from N, O, S, P, Se, and Te,
Preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group (for example, pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole,
Benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole,
A group derived from indole, quinoline, etc.), which is a substituent (same as the substituent when Q is an arylene group)
May be included, and the C number is preferably 2 to 15, and more preferably 2 to 10. The most preferable Q is a group represented by the following chemical formula 37.

[0092]

[Chemical 37]

It is

Therefore, the most preferred in the present invention-
(T) _k- X-Q- is a group represented by the following chemical formula 38.

[0095]

[Chemical 38]

It is

When R ₁₁ , R ₁₂ or R ₁₃ is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may have a substituent (eg halogen). Atom, hydroxyl, carboxyl, sulfo, phosphono, phosphine, cyano, alkoxy, aryl,
Alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl,
Sulfamoyl, sulfonyl) may be included.

When R ₁₁ , R ₁₂ or R ₁₃ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group and has an unsaturated bond even if it has a bridging group. However, it may have a substituent (the same as the substituent when R ₁₁ , R ₁₂ or R ₁₃ is an alkyl group).

When R ₁₁ , R ₁₂ or R ₁₃ is an aryl group, the aryl group may have a substituent (R ₁₁ ,
In addition to the substituents when R ₁₂ or R ₁₃ is an alkyl group, examples thereof include alkyl and cycloalkyl. ) May be included.

When R ₁₁ , R ₁₂ or R ₁₃ is a heterocyclic group, the heterocyclic group is at least one N, S, O, R, Se.
Or 3 to 8 containing a hetero atom selected from Te in the ring
Membered (preferably 5 to 7 membered) monocyclic or condensed ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), wherein the substituent (R ₁₁ , R ₁₂ or R ₁₃ is aryl) In the case of a group, it may have the same as the substituent).

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group. At this time, the counter ion may be, for example, Li ⁺ , Na.
⁺ , K ⁺ , and ammonium.

R ₁₁ is preferably a hydrogen atom, a carboxyl group, an alkyl group having a C number of 1 to 10 (for example, methyl, t-butyl, sulfomethyl, 2-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl,
Benzyl, ethyl, isopropyl) or C number 6-12
Is an aryl group (eg, phenyl, 4-methoxyphenyl, 4-sulfophenyl), particularly preferably a hydrogen atom, a methyl group or a carboxyl group.

R ₁₂ is preferably a cyano group, a carboxyl group, a carbamoyl group having a C number of 1 to 10, a sulfamoyl group having a C number of 0 to 10, a sulfo group, an alkyl group having a C number of 1 to 10 (eg methyl, sulfomethyl), A sulfonyl group having 1 to 10 C numbers (eg, methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 C numbers (eg, acetamide, benzamide), or a sulfonamide group having 1 to 10 C numbers (eg, methanesulfonamide, toluenesulfone) Amido), particularly preferably cyano group, carbamoyl group or carboxyl group.

R ₁₃ is preferably a hydrogen atom and has a C number of 1 to 12
An alkyl group of (for example, methyl, sulfomethyl, carboxymethyl, 2-sulfoethyl, 2-carboxyethyl,
Ethyl, n-butyl, benzyl, 4-sulfobenzyl)
Or an aryl group having a C number of 6 to 15 (eg, phenyl, 4
-Carboxyphenyl, 3-carboxyphenyl, 4-
Methoxyphenyl, 2,4-dicarboxyphenyl, 2
-Sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl), more preferably an alkyl group having 1 to 7 C atoms or 6 to 10 C atoms. Is an aryl group.

R ₁₄ is specifically an acyl group represented by the general formula (II) or a sulfonyl group represented by the general formula (III). General formula (II) R ₃₁ CO- General formula (III) When R ₃₁ SO ₂ -R ₃₁ is an alkyl group, the alkyl group may be linear or branched and may contain an unsaturated bond. Alternatively, a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino,
Ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₃₁ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, which may have a bridging group or an unsaturated bond, and may be substituted. Group (same as the substituent when R ₃₁ is an alkyl group)
May have.

When R ₃₁ is an aryl group, the aryl group, even if it is a condensed ring, has a substituent (in addition to the substituent when R ₃₁ is an alkyl group, there are alkyl, cycloalkyl, etc.). May be.

When R ₃₁ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered (preferably, heterocyclic group containing at least one hetero atom selected from N, S, O, P, Se or Te in the ring. 5
To 7-membered) monocyclic or condensed-ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) having a substituent (the same as the substituent when R ₃₁ is an aryl group). You may have.

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group. At this time, the counter ion may be, for example, Li ⁺ or Na.
⁺ , K ⁺ , and ammonium.

R ₃₁ is preferably an alkyl group having a C number of 1 to 10 (eg methyl, carboxymethyl, sulfoethyl, cyanoethyl), a cycloalkyl group having a C number of 5 to 8 (eg cyclohexyl, 2-carboxycyclohexyl), or C It is an aryl group of 6 to 10 (eg phenyl, 1-naphthyl, 4-sulfophenyl), and particularly preferably an alkyl group of 1 to 3 C's and an aryl group of 6 C's.

R ₁₅ is a substitutable group, preferably an electron donating group, and particularly preferably —NR ₃₂ R ₃₃ or —OR ₃₄ . The 4-position is preferable as the substitution position. R ₃₂ , R ₃₃ and R ₃₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and are the same as R ₃₁ . A ring may be formed between R ₃₂ and R ₃₃ , and the nitrogen heterocycle formed is preferably an alicyclic ring.

J represents an integer of 0 to 4, preferably 1 or 2, and particularly preferably 1.

When R ₁₆ or R ₁₇ is an alkyl group, the alkyl group may be linear or branched and may contain an unsaturated bond, and a substituent (eg, halogen atom, hydroxyl, Carboxyl, sulfo, phosphono,
Phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₁₆ or R ₁₇ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group having a bridging group or an unsaturated bond. Also may have a substituent (the same as the substituent when R ₁₆ or R ₁₇ is an alkyl group).

When R ₁₆ or R ₁₇ is an aryl group,
Even if the aryl group is a condensed ring, a substituent (R ₁₆ or R _16
In addition to a substituent when ₁₇ is an alkyl group, there are alkyl, cycloalkyl, etc.).

When R ₁₆ or R ₁₇ is a heterocyclic group, the heterocyclic group is a 3- to 5-membered ring containing at least one hetero atom selected from N, S, O, P, Se or Te in the ring. A (preferably 5 to 7 membered) monocyclic or condensed ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), which has a substituent (R ₁₆
Alternatively, when R ₁₇ is an aryl group, it may have a substituent).

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group. At this time, the counter ion may be, for example, Li ⁺ or Na.
⁺ , K ⁺ , ammonium and the like.

R ₁₆ is preferably a cyano group, a carboxyl group, a carbamoyl group having a C number of 1 to 10, an alkoxycarbonyl group having a C number of 2 to 10, an aryloxycarbonyl group having a C number of 7 to 11, and a C number of 0 to 10. Sulfamoyl group, sulfo group, C 1-10 alkyl group (eg methyl, carboxymethyl, sulfomethyl), C 1-10 sulfonyl group (eg methylsulfonyl, phenylsulfonyl), C 1-10 carbonamido group (Eg, acetamide, benzamide), a C 1-10 sulfonamide group (eg, methane sulfonamide, toluene sulfonamide), an alkyloxy group (eg, methoxy, ethoxy) or an aryloxy group (eg, phenoxy), and particularly preferably Cyano group, carbamoyl group, alkoxycarbonyl group, It is a carboxyl group.

R ₁₇ is preferably a hydrogen atom, and the C number is 1 to 1.
2 alkyl groups (eg methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl, 4
-Sulfobenzyl) or an aryl group having a C number of 6 to 15 (eg, phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2,4-dicarboxyphenyl, 4-
Sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl), more preferably an alkyl group having 1 to 7 C atoms or 6 to 10 C atoms.
Is an aryl group.

Specific examples of the yellow-colored cyan couplers of the present invention are shown in Chemical Formulas 39 to 48 below, but the present invention is not limited thereto.

[0121]

[Chemical Formula 39]

[0122]

[Chemical 40]

[0123]

[Chemical 41]

[0124]

[Chemical 42]

[0125]

[Chemical 43]

[0126]

[Chemical 44]

[0127]

[Chemical 45]

[0128]

[Chemical 46]

[0129]

[Chemical 47]

[0130]

[Chemical 48]

The yellow colored coupler represented by the general formula (CI) of the present invention is generally synthesized by a diazo coupling reaction between a 6-hydroxy-2-pyridone and an aromatic diazonium salt or a heterocyclic group diazonium salt containing a coupler structure. can do.

The former, that is, 6-hydroxy-2-pyridones are described in "Heterocyclic Compounds-Pyridine and its Derivatives-Part 3", edited by Klinsberg (Interscience Publishing, 1962), Journal of the American "Chemicals."・ Society (J.Am.Chem.Soc.) 194
3 years, 65 volumes, 449 pages, Journal of the Chemical Technology and Biotechnology (JC
hem.Tech.Biotechnol.) 1986, 36, 410
Tetrahedron, 1966, Vol. 22, p. 445, Japanese Patent Publication No. 61-52827, West German Patent No. 2,
162,612, 2,349,709, 2,9
No. 02,486, US Pat. No. 3,763,170 and the like.

The latter diazonium salt is described in US Pat.
04,929, 4,138,258, JP-A-61.
It can be synthesized by the method described in, for example, -72244 or 61-273543. 6-hydroxy-2-
The diazo coupling reaction between the pyridones and the diazonium salt is carried out in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, water or a mixed solvent thereof. Can be done. At this time, as the base, for example, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea, tetramethylguanidine can be used. Reaction temperature is usually −
The temperature is 78 ° C to 60 ° C, preferably -20 ° C to 30 ° C.

The following synthetic formulas 49 to 53 show synthetic routes for the colored couplers of the present invention.

[0135]

[Chemical 49]

[0136]

[Chemical 50]

[0137]

[Chemical 51]

[0138]

[Chemical 52]

[0139]

[Chemical 53]

Yellow-colored cyan couplers represented by formulas (CII) to (CIV) are described in JP-B-58-6939.
No. 1, JP-A-1-197563, and the method described in the above-mentioned patents and the like as a method for synthesizing the coupler represented by the general formula (CI).

In the present invention, the yellow colored cyan couplers represented by the general formulas (CI) and (CII) are more preferably used. Those represented by the general formula (CI) are particularly preferably used.

The yellow colored cyan coupler of the present invention is preferably added to the light-sensitive silver halide emulsion layer or a layer adjacent to the light-sensitive silver halide emulsion layer in the light-sensitive material, and particularly preferably to the red light-sensitive emulsion layer. The total amount to the sensitive material in is 0.005~0.30g / m ^2, preferably 0.02~0.20g / m ^2, more preferably 0.03 to
It is 0.15 g / m ² .

The yellow-colored cyan coupler of the present invention can be added in the same manner as a usual coupler as described later.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, and the like, and a color mixing inhibitor may be used as is usually used. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738 and 62-63936
It is also possible to arrange the layers in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. The layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- It is preferable to dispose the donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in the specification of 89850 adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains about 30 mol% or less of silver iodide, silver iodobromide, silver iodochloride, or iodochlorobromide. 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) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(Nov. 1979), p. 648, ibid. No. 307105 (Nov. 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, PhotographicScience by Gatov.
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 methods 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 forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process 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 corresponding portions are summarized in the table below. The light-sensitive material of the present invention comprises 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 mixed and used 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. No. 4,626,498, JP-A-59-214852, the inside of which is covered with a silver halide grain, and a colloidal silver is a photosensitive halogenated photosensitive grain. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in U.S. 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 inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. 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. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or number of silver halide grains is within ± 40% of the average grain size) It is preferable that the particles have a particle size of

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles in the 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 in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 page 5.fogging prevention page 24 ~ 25 page 649 page right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 page left columns 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. .. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Yellow couplers include, for example, U.S. Patents 3,933,501 and 4,02.
No. 2,620, No. 4,326,024, No. 4,401,752, No.
4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,973,968,
No. 4,314,023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897, and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No. 24220 (June 1984
Mon), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-71.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Those described in 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A 64-554, 64-555 and 64-556, and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye 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 a precursor group as a leaving group.
Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And the patents described in No. 307105 and VII-F, JP-A-57-151944, 57-154234, and 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in No. 4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-2201247 are effective for shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,1
No. 40, No. 2,131,188, JP-A Nos. 59-157638 and 59-1.
Those described in No. 70840 are preferable. In addition, JP-A-60-10
7029, 60-252340, JP-A-1-44940, 1-456
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 87 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 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers releasing dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate). (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, 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, dioctyl azetase Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention are, for example, 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, 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 a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 2, No. 2, pages 124 to 129 can be measured using a swellometer (swelling meter), and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after 3 minutes and 15 seconds of treatment 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.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is 150-500
% Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine 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-. 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 sulfuric acid Salt is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers include alkali metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic 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 pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. 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 with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH 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 specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 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
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; 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,
Iodide salt described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. 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. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
It is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably short as 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 impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method of improving the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to make the emulsion surface turbulent to further improve the stirring effect, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. 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. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society edited by "The Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. PH of washing water in the processing of the light-sensitive material of the present invention
Is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In 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, indoaniline-based compounds described in U.S. Pat. Metal salt complexes described, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various types of 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl-3-phenyl-3-phenyl-3- (phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-fluoro-3-bromo-3-chloro-3-bromo-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-bromo-3-amino-3-phenyl-3-phenyl-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-octyl-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-bromo-3-bromo-3-bromo-3-bromo-3-octyl-3-phenyl-3-chloro-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo 3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3-bromo-3- did lead;
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

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

[0164]

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

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.20 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.24 ExC-3 0.030 ExC-4 0.025 YC-1 0.017 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.78

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.185 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.030 YC-1 0.022 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.68

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.040 ExC-6 0.024 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

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

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.022 ExY-3 0.050 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

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

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

[0182]

[Table 1]

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

[0184]

[Chemical 54]

[0185]

[Chemical 55]

[0186]

[Chemical 56]

[0187]

[Chemical 57]

[0188]

[Chemical 58]

[0189]

[Chemical 59]

[0190]

[Chemical 60]

[0191]

[Chemical formula 61]

[0192]

[Chemical formula 62]

[0193]

[Chemical 63]

[0194]

[Chemical 64]

[0195]

[Chemical 65]

[0196]

[Chemical 66]

[0197]

[Chemical 67]

[0198]

[Chemical 68]

(Preparation of Sample 102) Sample 101 was prepared in the same manner as sample 101 except that the third and fourth layers YC-1 were replaced with equimolar YC-12. (Preparation of Samples 103 to 105) In Sample 102, ExC-1 of the third, fourth, and fifth layers was removed, and 0.5 of ExC-1 was used.
Sample 102 was prepared in the same manner as in Sample 102, except that the coupler shown in Table 2 was used. (Preparation of Samples 106 and 107) Sample 104 was prepared in the same manner as Sample 104 except that the third and fourth layers of YC-12 were replaced with the equimolar couplers shown in Table 2. (Preparation of Samples 108 and 109) Sample 105 was prepared in the same manner as Sample 105, except that the third and fourth layers of YC-12 were replaced with the equimolar couplers shown in Table 2.

(Preparation of Sample 110) Sample 104 was prepared in the same manner as Sample 104 except that ExC-3 of the fifth layer was replaced with equimolar Ia-21. (Production of Sample 111) In Sample 103, the third, fourth,
Prepared as Sample 103, except 5 layers of Ia-9 were replaced with equimolar comparative coupler A. Comparison coupler A
Is a structure shown below.

[0201]

[Chemical 69]

(Preparation of Sample 112) In Sample 103, the third and fourth layers of yellow-colored cyan coupler YC are used.
A sample was prepared in the same manner as the sample 103 except that -12 was omitted.

Samples 101 to 11 produced as described above
The following evaluations were performed using 1.

(Evaluation of Sensitivity) These samples were subjected to wedge exposure with white light, development processing was carried out in processing step 1 described below, and densities were measured. In the obtained characteristic curve, the cyan density is the cyan fog density +
It is shown by the logarithm of the reciprocal of the exposure amount that gives 0.10. (Based on sample 101)

(Evaluation of Color Turbidity) The sample was subjected to wedge exposure with red light, development processing was carried out in processing step 1, and the density of the processed sample was measured.
Minimum density magenta at the point of exposure giving a density of +2.0, and the values obtained by subtracting the minimum density value of magenta and yellow from the density value of the yellow (each D _G and D
_B ) was used as the color depth. The smaller these values are, the smaller the color saturation is and the better the color reproducibility is.

(Evaluation of storability of light-sensitive material) A sample was stored at 50 ° C for 8 hours.
The sample was allowed to stand for 5 days under the condition of 0% RH, and a aging test was performed. The samples before and after the aging test were subjected to the same exposure, development processing and density measurement as in (Evaluation of sensitivity), and the cyan density after the aging test was 1.2 after the cyan density before the aging test of each sample was 1.2. The storability of the light-sensitive material was evaluated by the concentration. The above results are summarized in "Table 2".

[0207]

[Table 2]

It can be seen that the light-sensitive material of the present invention has high sensitivity, little color turbidity, and good storage stability.

Processing Step 1 After exposing the color photographic light-sensitive material as described above, it is processed by an automatic developing machine by the method described below until the cumulative replenishment amount of the color developing solution becomes three times the capacity of the mother liquor tank. did. (Processing method) Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 45 ml 10 liters Bleaching 1 minute 00 seconds 38 ° C 20 ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ° C 30 ml 8 liters Washing (1) 40 seconds 35 ℃ 4 liters from (2) to (1) countercurrent piping system Washing with water (2) 1 minute 00 seconds 35 ℃ 30 ml 4 liters Stability 40 seconds 38 ℃ 20 ml 4 liters Dry 1 minute 15 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

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

(Bleaching solution) Common to tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) ₂ N-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -N (CH ₃ ) ₂ · 2HCl Ammonia water (27%) 15.0 ml Add water 1.0 liter pH 6.3

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-Add water 1.0 liter 1.0 liter pH 7.2 7.3

(Washing Solution) Tank Solution and Replenishing Solution Common Tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Was passed through a mixed bed column filled with to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

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

Example 2 No. 2 of Sample 9 of Example 3 of JP-A-2-93641,
ExC-1 of the 3rd and 4th layers was replaced with 0.7 times the molar amount of Exemplified coupler Ib-10 of the present invention, and ExC-4 of the 4th layer was replaced with equimolar amount of the exemplified coupler Ib-10 of the present invention. Two
1 and further includes the exemplary coupler YC-1 of the present invention.
2, 0.018 g / m ^{2 for} the third layer and 0.021 for the fourth layer
Sample 201 was prepared in the same manner as Sample 9 except that g / m ^{2 was} added. In Sample 201, the second, third, and fourth layers of Ib-10 were replaced with equimolar exemplary coupler IIIb-1, and the fourth layer of Ib-21 was replaced with equimolar exemplary coupler IIIb.
Sample 202 was prepared in the same manner as Sample 201 except that it was replaced with -2. Sample 9 produced in this way
When the samples 201 and 202 were tested and evaluated in the same manner as in Example 1, the sensitive material of the present invention had high sensitivity and small color turbidity,
It can be seen that the storability of the light-sensitive material is also good.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, and a cyan represented by the following general formula (1-a) or (1-b). A silver halide color photographic light-sensitive material comprising a coupler and a yellow-colored cyan coupler. [Chemical 1] (Wherein, Za is -NH- or -CH (R ₁₃₎ - represents, Zb and Zc each -C (R ₁₄₎ = or -N
Represents =. R ₁₁ , R ₁₂ and R ₁₃ each represent an electron-withdrawing group having a Hammett's 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 non-metal 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 represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine color developing agent. )