JP2879494B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic light-sensitive material having good color developability, excellent color reproducibility in all hues, and storage. And a silver halide color photographic material having little change in gradation.

[0002]

2. Description of the Related Art In a color printing paper, it is needless to say that the color reproducibility of a completed dye image is important in quality. How wide the color image obtained has the color gamut,
That is, how faithfully a reproduced image can be formed for a subject to be reproduced depends not only on the performance of a color negative film used for photographing, but also greatly depends on the color hue of a dye forming a print image. For this reason, studies on silver halide color photographic light-sensitive materials for printing excellent in color reproducibility have been conducted from various viewpoints. In general, a light-sensitive material for color printing uses a color reproduction method of a subtractive color method using cyan, magenta, and yellow as three primary colors, but the resulting color print can reproduce a wide range of colors with high fidelity. This is limited by the absorption properties of the cyan, magenta, and yellow dyes used. If the dye has a broad light absorption profile or undesired side absorption, color turbidity will result.

In view of the above, in order to form a cyan dye image in an ordinary color printing light-sensitive material, a commonly used phenol or naphthol coupler has side absorption in the green and blue regions. Therefore, there is a problem that color reproduction is not preferable, and it has been desired to solve this problem. As an example in which unnecessary side absorption deteriorates color reproduction, for example, when a green color of a green leaf is photographed with a color negative and a color print is produced, it may take on a greenish brown color. Also, the bright blue of the sky and the sea was sometimes yellowish. The present inventors have continued to study a silver halide color photographic light-sensitive material for printing which is improved in this point and has excellent color reproducibility.
As a means for solving this problem, EP 29
2,4-diphenylimidazoles described in 4,453A2 have been proposed. Dyes formed from these couplers have an undesired absorption on the short wavelength side smaller than conventional dyes, and are preferable in color reproduction.
However, these couplers also have insufficient color reproducibility, have low coupling activity, and have practical problems such as extremely low fastness to heat and light, and are not practically usable. Absent.

The pyrazoloazole couplers described in JP-A-64-553 and the like have improved short-wavelength absorption as compared with conventional dyes, but have sufficient color reproducibility as cyan couplers. However, there remains a problem that the coloring property is extremely low. Further, EP. 456
No. 226A1 discloses a pyrrolopyrazole-based cyan coupler as a coupler which gives a dye having an excellent hue. Although this coupler is an improved coupler in terms of color reproduction as compared with the above-mentioned cyan coupler, it is still insufficient, and has a drawback that color fogging is large in an unexposed area. In addition, the coloring properties did not reach a sufficiently satisfactory level.

[0005]

SUMMARY OF THE INVENTION The inventors of the present invention have developed a cyan coupler as described above, which is capable of achieving both the above-mentioned problems in the cyan coupler, that is, low undesired absorption in the green and blue regions and good color development. A pyrroloazole cyan coupler having a specific substituent as described below has been found. The cyan coupler forms a dye having excellent absorption characteristics, a dye having a large extinction coefficient and a sharp shape on the short wavelength side of the spectrum (having reduced undesired absorption in the green and blue regions), and has a coloring property, that is, It is preferable because it has high reactivity with the oxidized developing agent and excellent light and heat fastness of the produced dye. However, the present inventor made a color photographic paper using the above pyrroloazole-based cyan coupler, and as a result of further study, found an important practical problem. That is, the changes in sensitivity and gradation that occur during storage of the silver halide color photographic light-sensitive material are large.

As described above, when the above-mentioned pyrroloazole-based cyan couplers are put into practical use, the above-mentioned problems have to be solved in order to provide a silver halide color photographic light-sensitive material having stable performance to the market. Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material having good color developability, excellent color reproducibility in all hues, and having little change in sensitivity and gradation that occur during storage of the silver halide color photographic light-sensitive material. To provide.

[0007]

An object of the present invention is to provide a silver halide emulsion layer containing at least a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a yellow dye-forming coupler on a support. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a cyan dye-forming coupler, the silver halide emulsion layer containing the cyan dye-forming coupler contains at least a cyan dye-forming coupler represented by the following formula (Ia): The silver halide emulsion layer containing one kind and the cyan dye-forming coupler contains a compound represented by the following general formula (B), and a coating p of the silver halide color photographic light-sensitive material.
This is achieved by a silver halide color photographic material, wherein H is 4.0 to 6.5.

[0008]

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In the general formula (Ia), Za represents -NH- or -CH (R ₃ )-, and Zb and Zc each represent-
C _(R 4) = or an -N =. Where Za is -CH
_{(R 3)} - when it is, Zb is, -C _(R 4) = a and Zc is it is not -N =. R ₁ , R ₂ and R
₃ each have a Hammett's substituent constant σ _p value of 0.20
It represents the above electron-withdrawing group. Where σ _{p of} R ₁ and R ₂
The sum of the values is 0.65 or more. R ₄ represents a substituent . However, when two R ₄ are present in the formula, they may be the same or different. X
Represents a hydrogen atom or a group which is released by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. Even when the group of R ₁ , R ₂ , R ₃ , R ₄ or X becomes a divalent group and bonds to a dimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. Good.

[0010]

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In the general formula (B), A is -N = or -CH
= Represents R₁, R_Two, R_ThreeAnd R _FourAre the same
A substituted or unsubstituted alkyl group which may be different or different,
Substituted or unsubstituted alkylamino group, substituted or unsubstituted
Substituted arylamino group, substituted or unsubstituted aryloxy
Represents a group. X₁And X_TwoMay be the same or different
Child or -SO_ThreeM represents a hydrogen atom or water-soluble
Represents an atom or group of atoms that form a salt. In compounds
Keru-SO_ThreeThe sum of M groups is preferably 1 to 6.
No.

Hereinafter, the present invention will be described in detail. First, the compound of the present invention will be described in detail. The general formula (I) of the present invention
The cyan coupler represented by a) is specifically represented by the following general formulas (IIa) to (VIIIa).

[0013]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and X
Has the same meaning as in general formula (Ia). )
In the present invention, the compound represented by the general formula (IIa), (IIIa) or (IVa)
And a cyan coupler represented by the general formula (II)
Preference is given to cyan couplers represented by Ia).

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

R ₁ , R ₂ and R ₃ are each an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Preferably, a sigma _p value of 0.35 or more electron-withdrawing group, more preferably, sigma _p value of 0.60 or more electron withdrawing groups. The upper limit is an electron-withdrawing group of 1.0 or less. Hammett's rule is 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
Is an empirical rule proposed by LP Hammett
This is widely accepted today. The substituent constants determined by Hammett's rule include σ _p values and σ _m values, and these values are described in many general books.
For example, JA Dean ed. "Lange's Hand book of Chemis
try ", 12th edition, 1979 (Mc Graw-Hill) and" Chemical Area Special Issue ", No. 122, pp. 96-103, 1979
Know more about the year (Nankodo). In the present invention, R ₁ , R ₂ and R ₃ are defined by Hammett's substituent constant σ _p value, but are not limited to only those substituents having known values in the literature described in these books. Even if the value is unknown in the literature, it is, of course, included as long as it is within the range when measured based on the Hammett's rule.

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

The R ₁ , R ₂ and R ₃ are described in more detail. As the electron-withdrawing group having a σ _p value of 0.20 or more, an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4- Dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, N
-Phenylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N- (4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-
Propyloxycarbonyl, tert-butyloxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, diethylcarbamoylethoxycarbonyl, perfluorohexylethoxycarbonyl, 2-
Decyl-hexyloxycarbonylmethoxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl, 2,5-amylphenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (Eg, diphenylphosphono), diarylphosphinyl group (eg, diphenylphosphinyl), alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl), arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), alkyl A sulfonyl group (eg, methanesulfonyl, octanesulfonyl),
Arylsulfonyl group (for example, 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), alkyl halide groups (eg, trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogen Alkylamino group (eg, N, N-di- (trifluoromethyl) amino), halogenated alkylthio group (eg, difluoromethylthio, 1,1,2,2-tetrafluoroethylthio), and the σ _p value An aryl group (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) or a heterocyclic group (e.g., 2-benzoxa) Zolyl, 2-benzothiazolyl, 1-phenyl-2-
Benzimidazolyl, 5-chloro-1-tetrazolyl,
1-pyrrolyl), a halogen atom (for example, a chlorine atom or a bromine atom), an azo group (for example, phenylazo) or a selenocyanate group.

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

Preferred as R ₁ , R ₂ and R ₃ are an acyl group, an acyloxy group, a carbamoyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group, Examples include a halogenated aryloxy group, a halogenated aryl group, an aryl group substituted with two or more nitro groups, and a heterocyclic group. More preferably,
An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group.
More preferably, a cyano group, an alkoxycarbonyl group,
Aryloxycarbonyl and alkyl halide groups.

Particularly preferably, an alkoxycarbonyl group substituted by a cyano group, a fluorine atom, an alkoxycarbonyl group or a carbamoyl group, or an alkoxycarbonyl group having a linear, branched or ether bond, an unsubstituted or an alkyl group or an alkoxy group Is an aryloxycarbonyl group substituted with As a combination of R ₁ and R ₂ , R ₁ is preferably a cyano group and R ₂ is a fluorine atom, an alkoxycarbonyl group substituted with an alkoxycarbonyl group or a carbamoyl group, or a straight chain,
An alkoxycarbonyl group having a branched chain or an ether bond, an unsubstituted or aryloxycarbonyl group substituted with an alkyl group or an alkoxy group.

R ₄ represents a substituent (including an atom);
As the substituent, a halogen atom, an aliphatic group, an aryl group,
Heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylaryl 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 oxy Carbonyl 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, Rubokishi group, a nitro group, a sulfo group, and an unsubstituted amino group or the like. Alkyl groups contained in these groups, an aryl group or heterocyclic group may be further substituted with the substituents exemplified in R _4.

More specifically, R ₄ is a halogen atom (eg, a chlorine atom or a bromine atom), an aliphatic group (eg, a linear or branched alkyl group having 1 to 36 carbon atoms, an aralkyl group, an alkenyl group, an alkynyl group). Groups, cycloalkyl groups and cycloalkenyl groups, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- ｛2- [4-
(4-hydroxyphenylsulfonyl) phenoxy] dodecanamido {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-
(2,4-di-t-amylphenoxy) propyl), an aryl group (preferably having 6 to 36 carbon atoms, for example, phenyl, naphthyl, 4-hexadecoxyphenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl, 3- (2,4-ter
t-amylphenoxyacetamide) phenyl), a heterocyclic group (eg, 3-pyridyl, 2-furyl, 2-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), an alkoxy group (eg, methoxy, ethoxy,
2-methoxyethoxy, 2-dodecyloxyethoxy,
2-methanesulfonylethoxy), an aryloxy group (for example, 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 Group (eg, 2-benzimidazolyloxy, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), alkyl / aryl or heterocyclic thio group (eg, methyl

Ruthio, ethylthio, octylthio, tetradodecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-tert-butylphenoxy) propylthio, phenylthio, 2-butoxy-5-
tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,4-triazole-
6-thio, 2-pyridylthio), acyloxy groups (eg, acetoxy, hexadecanoyloxy), carbamoyloxy groups (eg, N-ethylcarbamoyloxy, N
-Phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (eg, dodecylsulfonyloxy), an acylamino group (eg, acetamido, benzamide, tetradecaneamide, 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), an alkylamino group (e.g., methylamino, butylamino,
Dodecylamino, dimethylamino, diethylamino, methylbutylamino), arylamino groups (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamidanilino, N-acetylanilino, 2-
Chloro-5- [α-2-tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino, 2-chloro-
5-dodecyloxycarbonylanilino), a ureido group (eg, methylureide, phenylureido, N, N-
Dibutylureido, dimethylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkenyloxy group (eg, 2-propenyloxy), formyl group , An alkyl aryl or a heterocyclic acyl group (eg, acetyl, benzoyl, 2,4-di-
tert-amylphenylacetyl, 3-phenylpropanoyl, 4-dodecyloxybenzoyl), alkyl / aryl or heterocyclic sulfonyl groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl groups (eg, octanesulfinyl, dodecyl) Sulfinyl, dodecanesulfinyl, dodecanesulfinyl, phenylsulfinyl, 3-pentadecylphenyl

Sulfinyl, 3-phenoxypropylsulfinyl), alkyl / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl,
Pentadecyloxycarbonyl), alkyl / aryl or heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino, 2,4-di-te
rt-butylphenoxycarbonylamino), a sulfonamide group (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butylbenzenesulfonamide),
A carbamoyl group (eg, N-ethylcarbamoyl, N,
N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group ( For example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl)
Sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), sulfamide group (eg, dipropylsulfamoylamino) ), Imide groups (eg, N-succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl groups (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy groups,
Examples include a cyano group, a carboxy group, a nitro group, a sulfo group, and an unsubstituted amino group.

R ₄ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. 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 include a sulfinyl group, a phosphonyl group, an acyl group, and an azolyl group. More preferably an alkyl group, an aryl group, more preferably at least one alkoxy group, a sulfonyl group, a sulfamoyl group,
An alkyl group or an aryl group having a carbamoyl group, an acylamide group or a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one acylamide group or sulfonamide group as a substituent.

In the general formula (Ia), X represents a hydrogen atom or a group capable of leaving when the coupler reacts with an oxidized form of an aromatic primary amine color developing agent (hereinafter referred to as "leaving group"); When X represents a leaving group, the leaving group may be a halogen atom, an aromatic azo group, an alkyl group, an aryl group, a heterocyclic group, an alkyl group, which is bonded to the coupling position via an oxygen / nitrogen / sulfur or carbon atom. An arylsulfonyl group, an arylsulfinyl group, an alkoxyaryloxy or heterocyclic oxycarbonyl group, an alkylaryl or heterocyclic carbonyl group '' or a heterocyclic group bonded to a coupling position at a nitrogen atom in a heterocyclic ring, for example, Halogen atom, alkoxy group, aryloxy group, acyloxy group, alkyl or aryl sulfo Ruoxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl / aryl or heterocyclic thio group, carbamoylamino group, arylsulfonyl group, arylsulfonyl group, 5- or 6-membered A nitrogen-containing heterocyclic group,
There are an imide group, an arylazo group, and the like, and the alkyl group, the aryl group, or the heterocyclic group included in these leaving groups may be further substituted with a substituent for R ₄ , and two or more of these substituents In this case, the substituents may be the same or different, and these substituents may further have the substituents described for R ₄ .

The leaving group is more specifically 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 group (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 group (for example,
Ethylthio, 2-carboxyethylthio, dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), arylsulfonyl group (eg, 2-butoxy-5-tert-octylphenylsulfonyl), arylsulfinyl group (eg, 2-butoxy-5-tert-)
Octylphenylsulfinyl), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 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 described as the substituents for R ₄ . As the leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. Desirable X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an arylsulfonyl group, an arylsulfinyl group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to a coupling active site with a nitrogen atom. . More preferably, it is an arylthio group.

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

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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The compounds of the present invention and their intermediates can be synthesized by known methods. For example, J. Am. Chem. Soc., 80, 5332 (1958), J. Am.
Ame. Chem., No. 81, 2452 (1959), J. Am. Chem.
Soc., 112, 2465 (1990); Org. Synth., I
270 (1941), J. Chem. Soc., 5149 (196)
2), Hetrocyclic., No. 27, 2301 (1988),
Rec. Trav. Chim., 80, 1075 (1961), the literature cited therein, or a similar method. Next, a specific synthesis example will be described. (Synthesis Example 1) Synthesis of Exemplified Compound (9) Exemplified Compound (9) was synthesized by the following route.

[0041]

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2-amino-4-cyano-3-methoxycarbonylpyrrole (1a) (66.0 g, 0.4 mol)
In a dimethylacetamide (300 ml) solution at room temperature at 3,5-dichlorobenzoyl chloride (2a) (8
3.2 g, 0.4 mol) and stir for 30 minutes. Add water and extract twice with ethyl acetate. The organic layer is collected, washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and acetonitrile (300 ml)
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 cooling with water, hydroxylamine-o-sulfonic acid (237 g, 2.1 mol) is added little by little while taking care not to raise the temperature rapidly, and the mixture is stirred for 30 minutes after the addition. 0.1N hydrochloric acid aqueous solution is dropped, and neutralized while looking at pH test paper. Extract three times with ethyl acetate, wash the organic layer with water and saturated saline, 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 obtain compound (4a) (9.50 g, 9%).

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

1.8 g of the obtained (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane, and 1.5 g was further dissolved.
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 washed with water. The ethyl acetate layer was dried, distilled off, and purified by residue column chromatography to obtain 1.6 g of the desired Exemplified Compound (9). Melting point 9
7-98 ° C.

When the cyan coupler of the present invention is applied to a silver halide color light-sensitive material, it is sufficient that the support contains at least one layer containing the coupler of the present invention.
The layer containing the coupler of the present invention may be a hydrophilic colloid layer on a support. A general color light-sensitive material can be constituted by coating a support with a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order. Although possible, the order may be different. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength region and a color coupler which forms a dye having a complementary color with the light to be exposed, thereby performing color reduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the color coupler may not have the above correspondence.

When the coupler of the present invention is applied to a light-sensitive material, it is particularly preferable to use it in a red-sensitive silver halide emulsion layer. The amount of the coupler of the present invention added to the light-sensitive material is generally from 1 × 10 ^-3 mol to 1 mol per mol of silver halide.
Mole, preferably 2 × 10 ^-3 mole to 5 × 10 ^-1 mole.

A preferred silver coating amount of the cyan color forming emulsion layer, 0.05~0.50g / m ² in terms of silver coating amount, more preferably from 0.10~0.30g / m ^2. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution is added to a coupler solution containing a surfactant,
It may be an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

As a dispersion medium of such a coupler, a dielectric constant (25 ° C.) of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.
7, a high-boiling organic solvent and / or a water-insoluble polymer compound can be preferably used. In the present invention, the ratio (weight) of the dispersion medium to the coupler is preferably 0.1.
-10, more preferably 2-7.

Next, the compound of the formula (B) of the present invention will be described in detail. In the general formula (B), R ₁ , R ₂ , R ₃
And R ₄ each represent a substituted or unsubstituted alkyl group (eg, 2-ethylamino-ethyl, methyl, ethyl, propyl, butyl), a substituted or unsubstituted alkylamino group (eg, methylamino, ethylamino, propylamino, Dimethylamino, diethylamino, dodecylamino, siloxyhexylamino, β-hydroxyethylamino, di- (β-hydroxyethyl) amino, β-sulfoethylamino), substituted or unsubstituted arylamino groups (eg, aniline, o-sulfoanilino) , M-sulfoanilino, p-sulfoianilino, o-toluidino, m-toluidino, p-toluidino, o-carboxyanilino,
m-carboxyanilino, p-carboxyanilino, o
-Chloroanilino, m-chloroanilino, p-chloroanilino, p-aminoanilino, o-anisidino, m-anisidino, p-anisidino, o-acetaminoanilino,
Hydroxyanilino, disulfophenylamino, naphthylamino, sulfonaphthylamino, benzylamino, o
-Anisylamino, m-anisylamino, p-anisylamino), or a substituted or unsubstituted aryloxy group (for example, phenoxy).

M is a hydrogen atom or an atom or group of atoms forming a water-soluble salt [eg, -NH ₄ , an alkali metal (Na, K
Etc.]]. Including the ones which are substituted in R _1, R _2, R ₃ and R _4, it is preferred that in the compounds has from 1 to 6 of the -SO ₃ M groups. Next, specific examples of the compound represented by the general formula (B) used in the present invention are shown, but the compound represented by the general formula (B) of the present invention is not limited to these.

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The compound represented by the general formula (B) is synthesized by a usual method described on page 8 of "Fluorescent Whitening Agent" (published in August 1976, edited by the Chemical Industry Association of Japan). be able to.

The compound represented by the general formula (B) used in the present invention can be directly dispersed in the emulsion, or can be dispersed in a suitable solvent (eg, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, Acetone or the like) or a mixed solvent using a plurality of these solvents can be added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye. General formula (B)
May be added to the emulsion prior to the addition of the sensitizing dye, or may be added later. Alternatively, the compound of the formula (B) and the sensitizing dye may be separately dissolved, and these may be separately and simultaneously added to the emulsion. After mixing these, they may be added to the emulsion.

The compound represented by the formula (B) is used in an amount of 2.0 × 10 ^-4 to 1.2 × 10 ⁴ per mol of silver halide.
It is preferable to use ^-2 mol. More preferably, 5.0 × 10 ^-4 mol to 6.0 mol per mol of silver halide.
× 10 ^-3 mol is used. When it is used in an amount of 1.2 × 10 ^-2 mol or more per mol of silver halide, a foreign matter may be deposited on the surface of the light-sensitive material and a failure such as spots may appear in a photographic image.

The phrase that the silver halide emulsion used in the present invention "consists of silver chloride or silver chlorobromide grains having a silver chloride content of 90 mol% or more" means that the average halogen of the silver halide grains contained in the emulsion of the present invention. 90 mol% or more of the composition is silver chloride, meaning that it is silver chloride or silver chlorobromide containing substantially no silver iodide. Here, "substantially free of silver iodide" means that the silver iodide content is preferably 1.0 mol% or less. The average halogen composition of the silver halide grains is preferably silver chloride or silver chlorobromide containing substantially no silver iodide, in which 95 mol% or more is silver chloride. Most preferably, it is silver chloride or silver chlorobromide containing substantially no silver iodide in which 99 mol% or more is silver chloride.

The silver halide grains of the present invention preferably have a localized phase having a silver bromide content of at least 10 mol% in a layered or non-layered form inside and / or on the surface of the silver halide grains. Such an arrangement of the localized layer having a high silver bromide content is preferably in the vicinity of the grain surface from the viewpoints of continuous processing suitability and further pressure characteristics. Here, “near the grain surface” means a position within 1/5 of the grain size of the silver halide grains to be used, as measured from the outermost surface. More preferably, the position is within 1/10 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The most preferable arrangement of the localized layer having a high silver bromide content is as follows.
A localized phase having a silver bromide content of at least more than 10 mol% is epitaxially grown at a corner of a cubic or tetradecahedral silver chloride grain.

The silver bromide content of the localized phase having a high silver bromide content is preferably more than 10 mol%, but if the silver bromide content is too high, it decreases when pressure is applied to the light-sensitive material. In some cases, characteristics unfavorable for a photographic light-sensitive material, such as causing a sense of sensation or a large change in sensitivity and gradation before and after continuous processing, may be imparted. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is preferably in the range of 10 to 60 mol%, and 20 to 5 mol%.
A range of 0 mol% is most preferred. The silver bromide content of the localized phase having a high silver bromide content can be determined by X-ray diffractometry (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) and the like. Can be used to analyze. The localized phase having a high silver bromide content is preferably composed of silver having a silver content of 0.1 to 20% of the total silver constituting the silver halide grains of the present invention, and 0.2 to 5%. More preferably, it is composed of silver. The interface between the localized phase having a high silver bromide content and other phases may have a clear phase boundary, or may have a transition region in which the halogen composition changes gradually. Good.

Various methods can be used to form such a localized phase having a high silver bromide content. For example,
A localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-sided mixing method or a simultaneous mixing method.
Further, a localized phase can be formed even by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. Or,
After mixing cubic or tetradecahedral silver halide host grains with silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content,
It is also preferable to form a localized phase having a high silver bromide content by ripening.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1. 1μ to 2μ is preferred. The particle size distribution is preferably a so-called monodisperse having a coefficient of variation (a value obtained by removing the standard deviation of the particle size distribution by the average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetrahedral or octahedral, or irregular crystals such as spherical or plate-like. Those having a shape or those having a composite shape thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, 50% of the particles having the regular crystal form are used.
The content is preferably 70% or more, more preferably 90% or more.

In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle in terms of circle / thickness) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains are preferably used. it can. The silver chlorobromide emulsion used in the present invention is described in Chimie et Phisique by P. Glafkides.
Photographique (Paul Montel, 1967), GFDuff
in Photographic Emulsion Chemistry (Focal Press, 1966); VLZalikman et al Making and Coat
ing Photographic Emulsion (Focal Press, 1964
) Can be prepared. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used.
A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, p in the liquid phase where silver halide is formed
A method of keeping Ag constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion dopants can be introduced during the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper,
Examples thereof include salts such as thallium, and salts or complex salts of Group VIII elements such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum. In particular, complex salts of the above Group VIII elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is
Usually, chemical sensitization and spectral sensitization are applied. For chemical sensitization, chemical sensitization using chalcogen such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization represented by gold sensitization, or reduction sensitization is used alone or in combination. be able to. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

The spectral sensitization applied to the silver halide emulsion used in the present invention is performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. As the spectral sensitizing dye used at this time, for example, Heterocycli by FM Harmer
c compounds -Cyanine dyes and related compounds (J
ohn Wiley & Sons (Now York, London), 1964)
Can be mentioned. Specific examples of compounds and spectral sensitization are described in JP-A-62-215.
No. 272, from page 22, upper right column to page 38, are preferably used.

The silver halide emulsion used in the present invention is used for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance.
Various compounds or their precursors can be added. Specific examples of these compounds are described in the above-mentioned JP-A-62-1987.
Those described on pages 39 to 72 of JP-A-215272 are preferably used. The emulsion used in the present invention is
This is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide photographic light-sensitive material of the present invention is generally prepared in addition to each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer. Each layer such as a layer, an intermediate layer, an ultraviolet absorber, a protective layer, and an antihalation layer is appropriately provided as necessary.

The coating pH of the light-sensitive material of the present invention is 4.0 to 4.0.
6.5, preferably in the range of 5.0 to 6.3.
When the film pH exceeds 6.5, the sensitivity change during storage of the photosensitive material is large, and the object of the present invention is hardly achieved. In addition, when the film pH is lower than 4.0, there is a practical problem that the sensitivity greatly changes with time from exposure of the photosensitive material to development.

The coating pH of the silver halide color photographic light-sensitive material of the present invention is the pH of all photographic layers obtained by coating a coating solution on a support, and does not always coincide with the pH of the coating solution. . The pH of the coating is as described in JP-A-61-24.
It can be measured by the following method as described in No. 5153. That is, (1) 0.05 cc of pure water is dropped on the surface of the light-sensitive material on which the silver halide emulsion is coated. Next, (2) After standing for 3 minutes, use a surface pH measurement electrode (GS
Measure the coating pH at -165F). Adjustment of the coating pH can be performed using an acid (for example, sulfuric acid or citric acid) or an alkali (for example, sodium hydroxide or potassium hydroxide) as necessary.

The light-sensitive material according to the present invention is preferably provided with a colored layer which can be decolorized by a development treatment between the support and the light-sensitive emulsion layer in order to improve the sharpness of an image. Light absorbers that can be decolorized by development include
Colloidal silver and dyes are preferred, but colloidal silver is more preferred. Colloidal silver is described, for example, in US Pat. No. 2,688,60.
Nos. 1, 459,563 and Belgian Patent No. 62
It can be produced according to the method described in 2,695. After preparation, the colloidal silver used in the present invention is desirably desalted to an electric conductivity of 1800 μs cm ⁻¹ or less. The amount of the colloidal silver-containing layer to be used is preferably 0.01 to 0.5 g, more preferably 0.05 to 0.5 g, per m ^{2 of} silver. Dyes preferably used in the present invention are described in EP 0,337,490 A2, pp. 27-76.

In another preferred embodiment, a dye and a cationic polymer for mordant thereof can be used. The cationic polymer for mordant is described in JP-A-2-84637, pp. 18-26. In another preferred embodiment, a fine powder dye that is substantially water-insoluble at least at pH 6 or lower but substantially water-soluble at least at pH 8 or higher can be contained. Specific examples of such fine powder dyes, methods of use, and preferable amounts thereof are described in JP-A-2-308244, pp. 4-13. In order to improve the sharpness of an image, titanium oxide surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) is added to the water-resistant resin layer of the support in an amount of 1%.
It is also preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high-boiling organic solvent. The high-boiling organic solvent has a melting point of 100 ° C. or less and a boiling point of 140 ° C. Any of the above water-immiscible compounds and a good solvent for the coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. Alternatively, cyan, magenta or yellow couplers can be impregnated with a loadable latex polymer (eg, U.S. Pat. No. 4,203,716) in the presence or absence of the high boiling organic solvent described above, or with a water-insoluble and organic solvent. It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 15 of U.S. Pat. No. 4,857,449.
And WO 12/723 of WO 88/00723.
The homopolymers or copolymers described on pages 30 to 30 are used, and more preferably a methacrylate-based or acrylamide-based polymer, particularly an acrylamide-based polymer, is preferable in terms of stabilizing a color image.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in EP 0,277,589 A2 together with a coupler. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining in the color developing solution and / or remains after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine-based color developing agent may be used simultaneously or alone, for example, after storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler with the coupler.

The light-sensitive material according to the present invention is provided with a fungicide, such as that described in JP-A-63-271247, in order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent. The support used for the photosensitive material according to the present invention may be a reflective support or a transmissive support, but for the purpose of the present invention, a reflective support is preferable. Further, a white polyester-based support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer for a display may be used. The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

Further, upon exposure, US Pat.
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to conventional color development processing. In the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing agent is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied to process this light-sensitive material As the additives for treatment and processing, those described in the following patent gazettes, in particular, EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

As a method for processing a silver halide color light-sensitive material, the methods described in JP-A-2-207250, page 27, upper left column to page 34, upper right column are preferably applied.

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EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 0 ° C., 3.3 g of sodium chloride and N,
1.0 cc of N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added and the temperature was raised to 68 ° C. Subsequently, a solution prepared by dissolving 100 g of silver nitrate in 400 cc of distilled water and a solution prepared by dissolving 34.4 g of sodium chloride in 400 cc of distilled water were added to the above solution over 45 minutes while maintaining the temperature at 68 ° C. Next, a solution prepared by dissolving 60 g of silver nitrate in 200 cc of distilled water and a solution prepared by dissolving 20.6 g of sodium chloride in 200 cc of distilled water were added and mixed over a period of 20 minutes while maintaining the temperature at 68 ° C. After desalting and washing with water at 40 ° C., 90 g of lime-processed gelatin was added, and the pAg was adjusted to 7.4 and the pH was adjusted to 6.5 with sodium chloride and sodium hydroxide.
Adjusted to 4. After raising the temperature to 50 ° C. to prepare an unripened silver chloride emulsion, a silver bromide localized phase corresponding to a silver bromide content of 0.6 mol% with respect to silver chloride is formed. Was subjected to sulfur sensitization. Further, spectral sensitization was performed by adding 3 × 10 ⁻⁵ mol per mol of silver halide of the red-sensitizing sensitizing dye shown below, and the spectrally sensitized emulsion was divided into three equal parts, and then the compound of the present invention was further added. (B-7) was added in an amount shown in Table 1 (0 mol, 2.5 × 10 ⁻³ per mol of silver halide).
Mol, 2.5 × 10 ^-2 mol). The silver chlorobromide emulsions thus obtained were designated as emulsions # 1 to # 3, respectively.

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With respect to the three types of emulsions # 1 to # 3 prepared as described above, the shape, size, and distribution of the grain size were determined from electron micrographs. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. All three types of emulsions # 1 to # 3 were cubic grains with sharp corners having a grain size of 0.5 μm and a grain size distribution of 0.09.

Next, in each of the above-described preparation methods of emulsions # 1 to # 3, the grain formation temperature was lowered to make the average grain size 0.4 μm and the grain size distribution 0.10, and the red-sensitized sensitization shown above was performed. The dye was used in an amount of 3. mole per mole of silver halide.
Emulsion # except that spectral sensitization was performed by adding 6 × 10 ^-5 mol
Emulsions # 4 to # 6 similar to 1 to # 3 were prepared, respectively.
X-ray diffraction analysis of emulsions # 1 to # 6 showed weak diffraction at a portion corresponding to silver bromide content of 10 mol% to 40 mol%. Therefore, in emulsions # 1 to # 6, the silver bromide content was 10 mol% to 4 mol% at the corners of the cubic silver chloride grains.
It can be said that 0 mol% of the localized phase is epitaxially grown.

Next, after a corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper (sample 101) having the layer configuration shown was produced. The coating solution was prepared as follows. Preparation of coating solution for fifth layer 13.2 g of cyan coupler (ExC), 7.2 g of ultraviolet absorber (UV-2), color image stabilizer (Cpd-1) 1
2.0 g, (Cpd-6) 0.4 g, (Cpd-8)
0.4 g, (Cpd-9) 6.0 g, (Cpd-10)
37.2 cc of ethyl acetate, 0.4 g of solvent (Solv-1) and 8.8 g of solvent (Solv-6) were added to 6.0 g and 0.4 g of (Cpd-11) and dissolved, and this solution was dissolved in dodecylbenzenesulfonic acid. After being added to 240 cc of a 10% aqueous gelatin solution containing 16 cc of sodium, the mixture was emulsified and dispersed with an ultrasonic homogenizer. A fifth layer coating solution was prepared by mixing and dissolving two types of emulsions (# 1 and # 4) having different sizes in the obtained dispersion. Coating solutions for layers other than the fifth layer were prepared in the same manner as for the fifth layer coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt and 1,2-bis (vinylsulfonyl) ethane were used. In addition, each layer contains C as a preservative.
The total amount of each of pd-14 and Cpd-15 is 25.0 mg.
/ M ² and 50.0 mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

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The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated amount in terms of silver. Support Polyethylene laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive yellow coloring layer) Silver chlorobromide emulsion (cube, average particle size) 6: 4 mixture (Ag molar ratio) of a large emulsion of 0.8 μm and a small emulsion of 0.6 μm, the coefficient of variation of the grain size distribution is 0.08 and 0.09, respectively. 4 mol% is locally contained in a part of the grain surface, and the remainder is silver chloride. Silver halide 0.27 Gelatin 1.16 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second layer (color mixture preventing layer) Gelatin 1.00 Color mixture inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.03 Solvent (Solv-3) 0.25 Solvent (Solv) -7) 0.25 Third layer (green-sensitive magenta color-forming layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-sized emulsion having an average grain size of 0.55 μm and small-sized emulsion having a size of 0.39 μm ( The variation coefficient of the grain size distribution is 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of AgBr is locally contained in a part of the grain surface, and the remainder is silver chloride. 0.13 gelatin 1.45 magenta coupler (ExM) 0.16 color image stabilizer (Cpd-5) 0.15 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd) -6) 0.01 stable color image (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15 Fourth layer (color mixture prevention layer) Gelatin Color mixture inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth layer (red-sensitive cyan coloring layer) Large size emulsion (# 1) 0.10 Small size emulsion (# 4) 0.10 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV -2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) ) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22 Sixth Layer (UV absorbing layer) Gelatin 0.55 UV absorber (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15 Seventh layer (protection) Layer) Gelatin 1.13 Acrylic-modified copolymer of polyvinyl alcohol (denaturation degree 1 7%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01 The compounds used herein are shown below.

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As described above, the sample 101 was obtained. In addition, in Sample 101, the value of the coating pH was 5.5.

(Preparation of Samples 102 to 123) Based on the photosensitive material (Sample 101) obtained as described above,
The pH of the first layer coating solution and the second layer coating solution are adjusted to H ₂ SO ₄ and Na
Samples 102 to 123 shown in Table 1 were obtained by changing the coating pH by changing the addition of OH, changing the cyan coupler and the emulsion in the fifth layer (red-sensitive cyan coloring layer). The emulsion of the fifth layer was a large-sized emulsion (# 1).
To # 3) and small-sized emulsions (# 4 to # 6) were mixed at a weight ratio of 1: 1.

First, the sample was subjected to gray exposure so that the developed silver amount became 30% of the applied silver amount, and a color developing tank was prepared using a liquid having the following processing steps and processing solution composition in a paper processing machine. Continuous processing was performed until replenishing twice the volume. Processing process Temperature Time Replenishment amount Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liters Bleaching and fixing 30-35 ° C 45 seconds 215 ml 17 liters Stable (1) 30-35 ° C 20 seconds −10 liters Stable (2) 30 to 35 ° C. 20 seconds - 10 liters stabilization (3) 30 to 35 ° C. 20 seconds 350 ml 10 l drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (rinse (3) from (1) The composition of each processing solution is as follows.

Color developer [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Chloride Sodium 1.4g-Potassium carbonate 25g 25g N-ethyl-N-([beta] -methanesulfonamidoethyl) -3-methyl-4-aminoallysine sulfate 5.0g 7.0g N, N-bis (carboxymethyl) hydrazine 4.0g 5.0g N, N-di (sulfoethyl) hydroxylamine · 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C.) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. 1000ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Deionized water (Calcium and magnesium are each 3ppm
Less than)

In order to examine the short-wavelength side absorption characteristics of the cyan coloring dye of the light-sensitive material obtained above, exposure was carried out for 1/10 second through a red filter and color development was performed. Then, using a commercially available spectrophotometer (UV-356, Shimadzu Corporation), an absorption spectrum was obtained with reference to the white plate.
The ratio of the absorbance at 450 nm to the absorbance at 0 nm was determined and used as a measure of side absorption. The smaller this value is, the smaller the side absorption is. Further, in order to evaluate the change in sensitivity during storage of the light-sensitive material, the sensitivity when each sample was exposed through an optical wedge and a red filter for 1/10 second was measured immediately after the application and at 50 ° C. and 80% humidity. After storage for days, the comparison was made and the change in sensitivity was evaluated. In the evaluation, the logarithm of the reciprocal of the amount of light required to give a density of fog + 1.0 was defined as S, and a difference (S) between the S was used. The closer this value is to 0, the smaller the change in sensitivity during storage. Further, an arbitrary position of each sample was cut out, and the range of 1 m ² was examined for the presence of solid precipitates of 100 μm or more. The results are summarized in Table 2.

[0107]

[Table 6]

[0108]

[Table 7]

From the results shown in Table 2, the effect of the present invention is clear. First, in the samples (101 to 109) using the comparative cyan coupler (ExC), the side absorption of the cyan coloring dye on the short wavelength side is high, which is not preferable in color reproduction. Samples (110 to 123) containing the cyan coupler of the present invention are preferable because the side absorption of the cyan coloring dye is low, but samples (110 to 11) not using the compound (B-7) of the present invention.
3) Or samples (116, 117, 121, 123) whose coating pH is out of the range of the present invention, and samples 101-101 using the cyan coupler for comparison whose sensitivity changes during storage.
108), which is not practical. Further, a large amount of the compound (B-7) of the present invention (2.5 mol / mol Ag)
(× 10 ⁻² mol), the change in sensitivity during storage tends to be slightly small, but is insufficient, and is accompanied by deterioration on the coated surface (samples 109, 118, and 11).
9), still not practical. When containing the cyan coupler of the present invention and the compound of the present invention and the coating pH is within the range of the present invention (samples 114, 115, and 12).
0, 122), a silver halide color photographic material satisfying both color reproducibility and storage stability can be obtained.

[0110]

According to the present invention, a silver halide color photographic light-sensitive material having excellent color reproducibility and little change in photographic properties during storage can be obtained.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 7/38 G03C 1/00-1/035 G03C 1/40

Claims (1)

(57) [Claims] 1. A support comprising a silver halide emulsion layer containing at least a cyan dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a yellow dye-forming coupler on a support. In a silver halide color photographic light-sensitive material, the silver halide emulsion layer containing the cyan dye-forming coupler comprises at least one cyan dye-forming coupler represented by the following formula (Ia) and the following formula (B): The silver halide emulsion layer containing at least one of the compounds represented by the formula (1), and wherein the silver halide emulsion layer contains a silver halide emulsion comprising silver chloride or silver chlorobromide having a silver chloride content of 90% mol or more; A silver halide color photographic light-sensitive material, wherein the coating pH of the photographic light-sensitive material is from 4.0 to 6.5. Embedded image (In the general formula (Ia), Za is -NH- or -CH (R
₃ ) —, wherein Zb and Zc are each —C (R ₄ )
= Or -N =. However Za is -CH _(R 3) -
, Zb is -C (R ₄ ) = and Zc is-
N = cannot be true. R ₁ , R ₂ and R ₃ 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 ₁ and R ₂ is 0.
65 or more. R ₄ represents a substituent . However, when two R ₄ are present in the formula, they may be the same or different. X represents a hydrogen atom or a group which is eliminated by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. R ₁ , R ₂ , R
The group of ₃ , R ₄ or X may be a divalent group and bond to a multimer or higher polymer or a polymer chain to form a homopolymer or a copolymer. ) (In the general formula (B), A represents -N = or = CH =.
R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkylamino group, an arylamino group, or an aryloxy group which may be the same or different. X ₁ and X ₂ may be the same or different and each represents a hydrogen atom or a —SO ₃ M group, and M represents a hydrogen atom or an atom or an atomic group forming a water-soluble salt. )