JP2840500B2 - 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 which is excellent in rapid processing property and color reproducibility and provides stable photographic properties with respect to composition fluctuation of a processing solution. Further, the present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a stable photographic performance with a small change in sensitivity over time of a coating solution.

[0002]

2. Description of the Related Art In recent years, demands for rapid processing performance improvement of color photographic paper have become increasingly strong, and much research has been conducted. It is known that increasing the silver chloride content of the silver halide emulsion used results in a dramatic improvement in the development speed. For example, see International Patent WO 87-0453.
No. 4, etc. In fact, high silver chloride emulsions used in color photographic papers have been developed in the market. In these photosensitive materials for color printing, it is needless to say that the color reproducibility of the resulting dye image is important in quality, in addition to the above-described rapid processing.
Whether the resulting color print has a wide color reproduction range, that is, how faithful the reproduced image can be composed for the subject to be reproduced, of course, depends on the performance of the color negative film used for shooting, It largely depends on the color hue of the dye forming the print image.
For this reason, research on silver halide color photographic light-sensitive materials for printing excellent in color reproducibility has been conducted from various viewpoints. In general, a light-sensitive material for color printing employs the color reproduction method of the decoloring method using cyan, magenta and yellow as three primary colors, but the finished color print can reproduce a wide range of colors with high fidelity. This is limited by the absorption characteristics 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 photographic material, a commonly used phenol-based or naphthol-based 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. As means for solving this problem, 2,4-diphenylimidazoles described in European Patent 294,453A2 have been proposed. Dyes formed from these couplers have a lower undesired absorption on the short-wave side than conventional dyes, and are preferable in color reproduction. However, these couplers also have practical problems such as poor color reproducibility, low coupling activity, and extremely low heat and light fastness. is not. The pyrazoloazole couplers described in JP-A-64-553 and the like have improved short-wavelength absorption as compared with conventional dyes, but the color reproducibility as a cyan coupler is sufficient. And the problem that the coloring property is extremely low remains.

[0004]

The present inventors have developed cyan couplers having excellent color reproducibility. As a result, pyrroazole type cyan dye-forming couplers having specific substituents described below have been used to produce green and green cyan couplers. It has already been found that a cyan dye having a significantly reduced undesired absorption can be formed in the blue region, and a dramatic improvement in color reproducibility can be achieved. However, when a color photographic material was prepared using this cyan dye-forming coupler having a pyrroloazole nucleus in combination with a high silver chloride emulsion and tested, serious practical problems that had not been expected before were found. Was done. That is, a silver halide color photographic light-sensitive material containing a cyan coupler can certainly obtain a cyan dye image with high color purity, but it is assumed that the silver dye color photographic light-sensitive material is developed in a lab (development laboratory) in the market. When a processing test was performed, a problem occurred in that a change in photographic properties (cyan image portion) due to a change in the composition of the processing solution was large.

Further examination of the factors of the composition change of the processing solution revealed that the degree of mixing of the bleach-fix solution into the developing solution corresponded to the change in photographic properties (cyan image portion). It is almost impossible to completely prevent the above-mentioned bleach-fix solution from being mixed into the developing solution even if strict control of the mixing is performed in a lab (development laboratory) in the market. Another problem is that the amount of bleach-fix solution mixed into the developer varies greatly depending on the lab due to differences in the roller transport and squeezing method of the automatic processor and the amount of processing per unit time. The trend is increasing. Since it is practically essential to always provide stable photographic performance in any lab in the market, it is necessary to minimize fluctuations in photographic characteristics due to the degree of mixing of the bleach-fix solution into the developer. ,
Technology development for that purpose was desired. Japanese Patent Application Laid-Open No. 62-254139 discloses a method for improving the stability of photographic characteristics against the incorporation of a bleach-fix solution into a developing solution by adding a phase having a relatively high silver bromide content to the outermost shell of high silver chloride grains. Techniques such as forming are disclosed, but the use of this technique did not reach a level sufficient for practical use. Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in rapid processability and color reproducibility, and which provides stable photographic properties even when the composition of a processing solution fluctuates.

On the other hand, in the case of a photosensitive material for color photographic paper, a large number of prints must be provided with a short delivery time and stable photographic performance. For this reason, photosensitive materials are continuously processed using an automatic developing machine, etc., but calcium deposits on rollers etc. during processing and scratches the photosensitive material surface, so that stable and uniform photographic performance can be maintained. There was another problem. Regarding calcium precipitated on rollers and the like during running processing, this calcium is released from the photosensitive material (mainly contained in gelatin) into the processing solution, and therefore the calcium content in the photosensitive material is reduced. It was necessary to minimize it. However, on the other hand, when a coating solution prepared using gelatin having a calcium content as small as possible is aged for several hours, especially in the case of a coating solution comprising a red-sensitive emulsion spectrally sensitized to a red region and a cyan dye-forming coupler. ,
There is also a problem that the sensitivity of the emulsion decreases over time, and in order to reduce the calcium content, it is necessary to overcome the instability of the production performance, and technical development for that purpose has been demanded. Therefore, another object of the present invention is to provide a silver halide color photographic light-sensitive material using an emulsion which does not have a problem that calcium is deposited on a roller or the like during a running process, and has a small decrease in sensitivity over time of a coating solution. It is in.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, they have found that the following silver halide color light-sensitive materials can solve the problems. That is, the present invention provides a photosensitive silver halide emulsion layer containing a cyan dye-forming coupler, a photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a photosensitive silver halide emulsion layer containing a yellow dye-forming coupler on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one layer and at least one non-photosensitive hydrophilic colloid layer, the silver halide emulsion layer containing the cyan dye-forming coupler is represented by the following general formula (I)
a) a silver halide containing at least one of the pyrroloazole-type cyan dye-forming couplers represented by a), and wherein the photosensitive silver halide emulsion is chemically sensitized with a gold compound and has a silver chloride content of 90 mol% or more; An object of the present invention is to provide a silver halide color photographic light-sensitive material characterized by being silver halide or silver chloride.

Embedded image (In the general formula (Ia), Za is -NH- or -CH
(R ₃ ) —, Zb and Zc each represent —C
(R ₄ ) = or -N =. R ₁ , R ₂ and R ₃
Represents 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 hydrogen atom or a substituent ( however, Za represents —NH—, Zb represents —N
= A, Zc is -C a (R ₄₎ =, to represent respectively
R ₄ represents an aliphatic group, an aryl group, an alkyl aryl
Or heterocyclic acyl group, alkyl / aryl or
Represents a heterocyclic oxycarbonyl group, a carbamoyl group, a sulf
An amoyl group, a hydroxy group, a cyano group or a nitro group
Represent. The alkyl and aryl groups contained in these groups are also
And rather the heterocyclic group is further substituted with another substituent
Is also good. ). 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. The group of R ₁ , R ₂ , R ₃ , R _4, or X becomes divalent and may form a homopolymer or a copolymer by bonding to a dimer or higher multimer or a polymer chain. . Further, the present invention provides a silver halide color photographic light-sensitive material characterized in that the total content of calcium atoms contained in the photographic constituent layer is 15 mg or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material. Is what you do. In the present invention, first, the calcium content will be described. As described above, the total content of calcium atoms contained in the photographic constituting layer of the silver halide color photographic light-sensitive material is 15 mg / m ² or less, preferably 10 mg / m ² or less. ² or less, and most preferably 8 mg / m ² or less. In the present invention, the amount of calcium contained in the silver halide color photographic light-sensitive material mainly depends on the amount of calcium contained in gelatin used as a binder. By using gelatin having a low calcium content, during the running process, there is no problem that calcium precipitates on rollers and the like.
Moreover, one of the major features of the present invention is that the use of the cyan dye-forming coupler of the present invention makes it possible to use gelatin having a calcium content as small as possible, with the decrease in the sensitivity of the emulsion being little over time of the coating solution. is there. Unless gelatin is used in which calcium in gelatin is specifically removed, generally 16 mg / m ² or more calcium is present in the light-sensitive material. In order to remove calcium in gelatin, an ion exchange resin, a dialysis treatment or the like is generally used.

Hereinafter, the compounds of the present invention will be described in detail. The pyrroloazole-type cyan dye-forming coupler represented by the general formula (Ia) of the present invention is specifically represented by the following general formulas (IIa) to (VIIIa).

[0009]

Embedded image

In the formulas (IIa) to (VIIIa), R ₁ , R ₂ , R
₃ , R ₄ and X have the same meanings as in general formula (Ia). In the present invention, general formulas (IIa) and (III)
A cyan coupler represented by a) or (IVa) is preferred, and a cyan coupler represented by formula (IIIa) is particularly preferred.

In the cyan coupler of the present invention, R ₁ , R ₂ and R ₃ each have a Hammett's substituent constant σ _p value of 0.3.
20 or more electron-withdrawing groups, and σ _{p of} R ₁ and R ₂
The sum of the values is 0.65 or more. The sum of the σ _p values of R 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 σ _p value of 0.20 or more. Preferably, σ
_p value is 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 was introduced in 1935 by LP Hammet in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
A rule of thumb proposed by mett, which 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
"Lange's Handbook of Chemistry", 12th edition, 19
1979 (McGraw-Hill) and "Chemical Area Special Edition", 122
No. 96-103, 1979 (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 described in these books. It goes without saying that even if the value is unknown in the literature, it is included as long as it is within the range when measured based on the Hammett's rule.

Specific examples of R ₁ , R ₂ and R ₃ which are electron-withdrawing groups having a σ _p value of 0.20 or more include an acyl group,
Acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, dialkylphosphono, diarylphosphono, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, aryl Sulfonyl 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 σ _p value of 0.20 or more, a heterocyclic group, a halogen atom, an azo group or a seleno And cyanate groups. Among these substituents, the group that can have a substituent may further have a substituent such as that described later for R ₄ .

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,
Acyl groups (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), acyloxy groups (eg, acetoxy), carbamoyl groups (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 (For example, diphenylphosphono), a dialkoxyphosphoryl group (for example, dimethoxyphosphoryl), a diarylphosphinyl group (for example, diphenylphosphinyl), an alkylsulfinyl group (for example, 3-phenoxypropylsulfinyl), an arylsulfinyl group ( For example, 3
-Pentadecylphenylsulfinyl), an alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), an arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), a sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), an acylthio group (eg, , Acetylthio, benzoylthio), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide Groups (eg, trifluoromethyl, heptafluoropropyl), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogenated alkylamino groups (eg, N, N-
Di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2
2-tetrafluoroethylthio), an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.20 or more (for example,
2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example,
2-benzoxazolyl, 2-benzothiazolyl, 1-
Phenyl-2-benzimidazolyl, pyrazolyl, 5-
Represents a 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 group (0.92),
Methanesulfonyl group (0.72), benzenesulfonyl group (0.70), methanesulfinyl group (0.49),
Carbamoyl group (0.36), methoxycarbonyl group (0.45), pyrazolyl group (0.37), methanesulfonyloxy group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) ).

Preferred as R ₁ , R ₂ and R ₃ are acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl,
Arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfamoyl, halogenated alkyl, halogenated alkyloxy, halogenated alkylthio, halogenated aryloxy, halogenated aryl, substituted with two or more nitro groups Aryl groups and heterocyclic groups. More preferred are an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. More preferred are a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a halogenated alkyl group.

Particularly preferred is 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, unsubstituted or an alkyl group or an alkoxy group. It is a substituted aryloxycarbonyl group. 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 hydrogen atom or a substituent (including an atom); examples of the substituent include 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 a substituent as exemplified for R ₄ .

More specifically, R ₄ is a hydrogen atom, 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). Group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} 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-hexadecyloxyphenyl, 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), alkoxy groups (eg, methoxy,
Ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy,
4-tert-butylphenoxy, 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), complex Ring oxy groups (eg, 2-benzimidazolyloxy, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), alkyl / aryl or heterocyclic thio groups (eg, methylthio, ethylthio, octylthio, tetradecylthio, 2-decylthio, 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 (eg, trimethylsilyloxy, dibutylmethylsilyloxy), a sulfonyloxy group (eg, dodecylsulfonyloxy), an acylamino group (eg, acetamido, benzamido, tetradecanamido, 2- (2,4
-Tert-amylphenoxy) acetamide, 2- [4-
(4-hydroxyphenylsulfonyl) phenoxy] decanamide, isopentadecaneamide, 2- (2,4-
Di-t-amylphenoxy) butanamide, 4- (3-
t-butyl-4-hydroxyphenoxy) butanamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, dimethylamino, diethylamino, methylbutylamino), an arylamino group (eg, phenylamino, 2-chloroanilino, 2- Chloro-
5-tetradecanamidoanilino, N-acetylanilino, 2-chloro-5- [α-2-tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino, 2-
Chloro-5-dodecyloxycarbonylanilino), a ureido group (for example, methylureide, phenylureido,
N, N-dibutylureido, dimethylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkenyloxy group (eg, 2-propenyloxy) ), Formyl groups, alkyl aryl or heterocyclic acyl groups (eg, acetyl, benzoyl, 2,4
-Di-tert-amylphenylacetyl, 3-phenylpropanoyl, 4-dodecyloxybenzoyl), alkyl aryl or heterocyclic sulfonyl groups (e.g. methanesulfonyl,

Octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyl / aryl or heterocyclic sulfinyl groups (for example, octanesulfinyl, dodecanesulfinyl, phenylsulfinyl, 3
-Pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), alkyl / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl,
Octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), alkyl / aryl or heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino, phenoxycarbonylamino,
2,4-di-tert-butylphenoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-tert-butyl) Benzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-
Di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group (eg, 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 (for example, imidazolyl,
Pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy, cyano, carboxy,
Examples include 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 a heterocyclic thio group. Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, imide group, Examples include a sulfinyl group, a phosphonyl group, an acyl group, and an azolyl group. More preferred are an alkyl group and an aryl group, and more preferred are an alkyl group and an aryl group having at least one alkoxy group, a sulfonyl group, a sulfamoyl group, 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. However, if Za is
-NH-, Zb represents -N =, Zc represents -C (R ₄ ) =
R ₄ represents an aliphatic group, an aryl
Group, alkyl / aryl or heterocyclic acyl group,
Alkylaryl or heterocyclic oxycarbonyl group,
Carbamoyl, sulfamoyl, hydroxy,
Represents an ano group or a nitro group. The functions included in these groups
An alkyl group, an aryl group or a heterocyclic group is
It may be substituted with a substituent. Specific examples of these groups and
Examples include the specific examples described above.
Preferred groups, more preferred groups, and particularly preferred groups
Examples of the groups include the groups described above.

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 includes a halogen atom, an aromatic azo group, an alkyl group, an aryl group, a heterocyclic group, an alkyl group bonded to the coupling position via an oxygen / nitrogen / sulfur or carbon atom. Or an arylsulfonyl group, an arylsulfinyl group, an alkoxyaryloxy or heterocyclic oxycarbonyl group, an aminocarbonyl group, an alkylaryl or a heterocyclic carbonyl group, or a heterocyclic ring bonded to the coupling position with a nitrogen atom in the heterocyclic ring A halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl Or an arylsulfonyloxy group, an acylamino group, an alkyl or arylsulfonamide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl / aryl or heterocyclic thio group, a carbamoylamino group, an arylsulfinyl group, an arylsulfonyl group, 5 Member or 6
Membered nitrogen-containing heterocyclic group, imide group, arylazo group, and the like, and the alkyl group, aryl group, or heterocyclic group contained in these leaving groups may be further substituted with a substituent at R ₄ . When two or more of these substituents are the same or different, these substituents
_It may have the substituents mentioned in ₄ .

The leaving group is more specifically a halogen atom (eg, a fluorine atom, a chlorine atom, a 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 . Further, as a 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 containing a polymer chain is represented by the general formula (I
It is an addition polymer having a cyan coupler residue represented by a), and a homo- or copolymer of an ethylenically unsaturated compound is a typical example. 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.

[0026]

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[0027]

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[0028]

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[0029]

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[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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The compounds of the present invention and their intermediates can be synthesized by known methods. For example, J. Am. Chem. Soc., No. 80, 5332 (1958),
J. Am. Chem. Soc., 81, 2452 (1959), JA
m. Chem. Soc., 112, 2465 (1990), Org. S
ynth., I, 270 (1941), J. Chem. Soc., 514.
9 (1962), Heterocycles, No. 27, 2301 (1
988), Rec. Trav. Chim., 80, 1075 (196)
The compound can be synthesized by the method described in 1) or the like, 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.

[0037]

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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 with 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 m
l) Compound (3a) (113 g, 8
4%).

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 (9
ml), followed by triphenylphosphine (5.7).
(6 g, 22 mmol) and heated under reflux for 8 hours. After cooling,
Add water and extract 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 (5a) and 12.4 g of (6a) were dissolved in 2.0 ml of sulfolane.
5 g of titanium isopropoxide 1.5 g were 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 was 97-98 ° C.

When the cyan coupler of the present invention is applied to a silver halide color light-sensitive material, it is sufficient that at least one layer containing the coupler of the present invention is provided on a support.
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. Further, the preferred coating amount of the cyan coupler of the present invention is from 2.0 × 10 ^-6 mol to 2.0 × 10 ^-6 mol / m ² of the light-sensitive material.
The amount is 10 ⁻³ mol, and more preferably 2.0 × 10 ⁻⁵ mol to 1.0 × 10 ⁻³ mol. The cyan coupler of the present invention can be arbitrarily mixed and used with a cyan coupler other than the present invention. The use ratio of the cyan coupler of the present invention is preferably 5 mol% or more, and more preferably 30 mol% or more.

The halogen composition of the silver halide emulsion grains coexisting with the cyan coupler of the present invention has a silver chloride content of 90%.
It must be at least mol%. Further, it is preferable that 95 mol% or more of the total silver halide constituting the silver halide grains is silver chloride which is substantially free of silver iodide or silver chloride which is silver chloride. Here, "contains substantially no silver iodide" means that the silver iodide content is 1.0 mol% or less. More preferred halogen composition of the silver halide grains is 9% of the total silver halide constituting the silver halide grains.
At least 8 mol% is silver chlorobromide or silver chloride substantially free of silver iodide, which is silver chloride. The silver halide emulsion grains coexisting with the cyan coupler of the present invention preferably have a localized phase in which the silver bromide content exceeds at least 10 mol%. Such an arrangement of the localized phase having a higher silver bromide content than that of the substrate (hereinafter, referred to as a silver bromide localized phase) is required to further exert the effects of the present invention. From the viewpoint of dependence and the like, it is necessary to be near the particle surface. 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. The position is preferably 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 silver bromide localized phase is such that a localized phase having a silver bromide content of at least more than 10 mol% is epitaxially grown at the corners of cubic or tetradecahedral silver chloride grains.

The silver bromide content of such a silver bromide localized phase preferably exceeds 10 mol%, but if the silver bromide content is too high, desensitization occurs when pressure is applied to the light-sensitive material. In some cases, characteristics unfavorable for a photographic light-sensitive material may be imparted, for example, causing a change in sensitivity or gradation due to a change in the composition of the processing solution. The silver bromide content of the silver bromide localized phase takes these points into account,
The range of 10 to 60 mol% is preferable, and 20 to 50 mol%.
Is most preferable. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen) or the like. be able to. The silver bromide localized phase is preferably comprised of silver in an amount of 0.1 to 20% of the total silver constituting silver halide emulsion grains coexisting with the cyan coupler of the present invention, and 0.5 to 7%. More preferably, it is composed of silver. The interface between such a silver bromide localized phase and other phases in the grains may have a clear phase boundary or may have a transition region in which the halogen composition changes gradually. . Various methods can be used to form such a silver bromide localized phase. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Further, a localized phase can also be formed by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. For example, a cube or 1
A water-soluble bromide solution is added to the tetrahedral silver halide host grains, or silver chlorobromide or silver bromide fine grains having a smaller average grain size than the silver halide host grains and a high silver bromide content are used. After mixing, ripening can form a silver bromide localized phase.

The formation of the silver bromide localized phase is preferably carried out in the presence of an iridium compound. Here, performing the formation of the localized phase in the presence of the iridium compound refers to supplying the iridium compound simultaneously with, immediately before, or immediately after the supply of silver or halogen for forming the localized phase. . For example, when a silver bromide localized phase is formed by adding a water-soluble bromide solution, it is preferable to add an iridium compound to the solution in advance, or to add another solution containing the iridium compound at the same time. Done. When a silver bromide localized phase is formed by mixing silver halide fine grains having a smaller average grain size than the silver halide host grains and having a higher silver bromide content and then ripening, the silver bromide-containing phase is contained. It is also preferable to incorporate an iridium compound in the silver halide fine grains having a high ratio in advance. The iridium compound may be present during the phase formation other than the formation of the silver bromide localized phase, but the silver bromide localized phase is preferably formed together with at least 50% of the total iridium added. Most preferably, it is formed with at least 80% of the total iridium added.

The silver halide grains of the present invention may have (100) planes, (111) planes, or both on the outer surface. May further include a higher-order plane, but is preferably a cube or a tetradecahedron mainly composed of (100) planes. The size of the silver halide grains of the present invention may be within the range usually used, but preferably the average grain size is from 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size distribution indicating the degree of monodispersion is preferably 0.2 or less as a ratio (s / d) between the standard deviation (s) in statistical analysis and the average particle size (d).
More preferably, it is 15 or less. It is also preferable to use a mixture of two or more monodisperse emulsions.

The silver halide emulsion containing a cyan coupler of the present invention must be chemically sensitized with a gold compound. The gold compound used may have a monovalent or trivalent gold oxidation number, and may be of various types. Gold compounds can be used.
Typical examples are tetrachloroauric (III) acid, tetracyanoaurate (III) acid or tetrakis (thiocyanato) aurate (III) acid or an alkali metal salt thereof, bis (thiosulfato) aurate (I) acid salt, dimethyl chloride Rhodanate gold (I) Gold complex ion or complex salt can be mentioned. The amount of the gold compound to be added is generally in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol, preferably in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol, per mol of silver halide. And more preferably in the range of 1 × 10 ^-6 to 1 × 10 ^-4 mol. The addition of these gold compounds is performed during the preparation of the silver halide emulsion, but is preferably performed until the completion of the chemical sensitization. In the silver halide emulsion used in the present invention,
By adding at least one of the mercapto-based compounds disclosed in JP-A-3-233448 and the like, it is possible to significantly prevent an increase in fog, particularly when a gold sensitizer is used. The addition may be carried out at the time of grain formation, desalting, chemical ripening or just before coating. However, it is preferably added at the grain forming, desalting and chemical ripening, especially before the addition of the gold sensitizer. The addition amount of the mercapto compound is from 1 × 10 ⁻⁶ to 1 mol of silver halide.
5 × 10 ⁻² mol is preferable, and 1 × 10 ⁻⁴ to 1 × 1 is more preferable.
0 ^-2 mol is preferred. There is no particular restriction on the location of addition,
It may be either a photosensitive layer or a non-photosensitive layer. The method of addition is not particularly limited, and may be any of during physical ripening during silver halide grain formation, during chemical ripening, and during preparation of a coating solution.

In the photographic material according to the present invention, the hydrophilic colloid layer can be decolorized by the processing described in EP 0,337,490 A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, and dihydric alcohols (2 to 4) are added to the water-resistant resin layer of the support. Titanium oxide surface-treated with, for example, trimethylolethane)
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The high-boiling organic solvents for photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are compounds having a melting point of 100 ° C. or less and a melting point of 140 ° C. or more and are immiscible with water. Any solvent 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 may 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 may be insoluble in water. Further, it can be dissolved in a polymer soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 1 of U.S. Pat. No. 4,857,449.
Homopolymers or copolymers described in column 5 and pages 12 to 30 of WO 88/00723 are preferably used, and more preferably a methacrylate or acrylamide polymer, especially an acrylamide polymer is used. It is preferable from the viewpoint of image stabilization.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler or a pyrroloazole coupler is preferable. That is, the compound (F) which forms a chemically inactive and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining 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 color developing agent can be used simultaneously or alone, for example, in 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 or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

Further, as a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.1 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 35 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be either low illuminance exposure or high illuminance short exposure, but for the present invention, an exposure method in which the exposure time per pixel is shorter than 10 ^-3 seconds is preferable, and a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds. Is more preferred.

Also, 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, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution 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 the processing method applied for processing 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.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

As the cyan coupler, in addition to the cyan coupler of the present invention and the diphenylimidazole cyan coupler described in JP-A-2-33144, European Patent E
P0,333,185A2, 3-hydroxypyridine-based cyan couplers (among others, couplers obtained by giving a chlorine leaving group to a 4-equivalent coupler (42) of coupler (42) listed as specific examples), and couplers (6 ) And (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are particularly preferred.
May be used in combination.

A method for processing a silver halide color light-sensitive material using a high silver chloride emulsion having a silver chloride content of 90 mol% or more is described in JP-A-2-207250, page 27, upper left column to upper right, page 34. The method described in the column is preferably applied.

[0065]

EXAMPLES The present invention will be specifically described below with reference to examples.
However, the present invention is not limited to this. Example 1 32 g of lime-processed gelatin was added to 800 ml of distilled water,
After dissolution at 40 ° C., 5.8 g of sodium chloride and N,
N'-dimethylimidazolidin-2-thione (1% aqueous solution
Liquid) 1.0 ml was added and the temperature was raised to 53 ° C.
Subsequently, a solution prepared by dissolving 80 g of silver nitrate in 480 ml of distilled water was used.
Dissolve 27.6 g of sodium chloride in 480 ml of distilled water
And the above solution over 60 minutes while maintaining the temperature at 53 ° C.
And mixed. Next, 80 g of silver nitrate was added to 300 m of distilled water.
and 24.3 g of sodium chloride and
4 mg of potassium sassianoferrate (II) trihydrate was added to 30 parts of distilled water.
The solution dissolved in 0 ml is kept at 53 ° C. for 20 minutes.
And mixed. Desalting and washing at 40 ° C
After that, add 90 g of lime-processed gelatin and further add sodium chloride
PAg to 7.4 with lithium and sodium hydroxide,
The pH was adjusted to 6.4. After raising the temperature to 58 ° C,
Localization of silver bromide on emulsion grain surface by adding 0.45 g of lithium
Phase and then optimally sulfurized with triethylthiourea.
Yellow sensitization was applied. Also, a red-sensitive sensitizing dye shown below
3 × 10 5 per mole of silver halide ^-FourAdd mole and min
Photosensitization was applied. Silver chlorobromide emulsion thus obtained
To emulsion R₁And

[0066] The emulsion R _1, instead of the sulfur sensitization alone by triethylthiourea uric acid, triethyl thiourea and 5 × 1
Only 0 ^-6 mole to gold-sulfur sensitization by chloroauric acid was prepared differently Emulsion R _2. Emulsion R ₁ is silver emulsion 1 instead of sulfur sensitization with triethylthiouric acid.
Only subjected to gold sensitization by mole per 2 × 10 ^-5 moles of chloroauric acid was prepared differently Emulsion R _3. In the same manner as described above, an emulsion having a desired particle size is prepared by changing the reaction temperature, and a blue-sensitive sensitizing dye and a green-sensitive sensitizing dye are added instead of the red-sensitive sensitizing dye, respectively. Thus, emulsions B1, B2 and G1, G2 were prepared. After performing corona discharge treatment on the surface of the paper support laminated on both sides with polyethylene, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was provided, and further various photographic constituent layers were applied, and the layer constitution shown below was obtained. A multilayer color photographic paper (sample 101) was produced. The coating solution was prepared as follows. Preparation of Coating Solution for Fifth Layer 35.0 g of cyan coupler (ExC), 14.0 g of sodium dodecylbenzenesulfonate, 100 ethyl acetate
ml, UV absorber (UV-2) 19.0 g, color image stabilizer (Cpd-8) 1.1 g, color image stabilizer (Cpd-9)
1.1 g, color image stabilizer (Cpd-10) 1.1 g, color image stabilizer (Cpd-11) 1.1 g, color image stabilizer (Cpd)
-12) 1.1 g, solvent (Solv-1) 1.1 g and solvent (Solv-6) 23.3 g were added and dissolved, and this solution was emulsified and dispersed in a 10% aqueous gelatin solution by a high-speed stirring emulsifier to emulsify. Dispersion A was prepared. The emulsified dispersion A and the the silver chlorobromide emulsion R ₁ were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below. Coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As the gelatin hardener for each layer, 1-oxy-3,
5-Dichloro-s-triazine sodium salt was used.
Further, Cpd-15 and Cpd-16 were added to each layer so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively. The silver chlorobromide emulsion of each photosensitive emulsion layer, the particle size was prepared in the same preparation method as the silver chlorobromide emulsion R _1, were used, respectively, the following spectral sensitizing dyes.

[0067]

[Table 6]

[0068]

[Table 7]

[0069]

[Table 8]

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer,
1- (5-methylureidophenyl)
-5-mercaptotetrazole is replaced by silver halide
3.4 × 10 per mole^-FourMol, 9.7 × 10^-FourMole,
5.5 × 10^-FourMole was added. The blue-sensitive emulsion layer and the green
4-hydroxy-6-methyl-1,
Halogenate 3,3a, 7-tetrazaindene
1 × 10 per mole of silver ^-FourMole and 2 × 10^-FourMole was added.
The following dyes are added to the emulsion layer to prevent irradiation.
(A coating amount is shown in parentheses).

[0071]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). However, the silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper (Central surface average roughness SR _A =
0.12 μm) [The first layer side polyethylene contains a white pigment (containing 14% by weight of TiO ₂ ) and a bluish dye (ultramarine)] First layer (blue-sensitive layer emulsion layer) Silver chlorobromide emulsion (cube, A 5: 5 mixture (silver molar ratio) of a large-size emulsion B1 having an average grain size of 0.80 μm and a small-size emulsion B2 having an average grain size of 0.85 μm, and the variation coefficients of the grain size distribution are 0.08 and 0.09, respectively. In both the size emulsions, 0.4 mol% of silver bromide is locally contained in a part of the grain surface, and the rest consists of silver halide grains of silver chloride.) 0.27 Gelatin 1.36 Yellow coupler (ExY) 0. 79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv- 2) 0.13

Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Third layer (green sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 6: 4 mixture (silver molar ratio) of large-size emulsion G1 having an average grain size of 0.55 μm and small-size emulsion G2 having an average grain size of 0.59 μm) Variation coefficient of grain size distribution Are 0.10 and 0.08, respectively. Each emulsion is composed of silver halide grains in which 0.8 mol% of silver bromide is locally contained on 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-6) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image Stabilizer (Cpd-8) 0.01 Color image stabilizer Cpd-9) 0.08 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fourth layer (color mixture preventing layer) Gelatin 0.70 Color mixture inhibitor (Cpd-4) 0.04 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv) -3) 0.18 fifth layer (red-sensitive emulsion layer) the silver chlorobromide emulsion R ₁ 0.20 gelatin 0.85 cyan coupler (ExC) 0.33 UV absorber (UV-2) 0.18 color Image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Color image stabilizer (Cpd-12) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer Agent (Cpd-8) 0.01 Solvent (Solv-6) 0.22 Solvent (Solv-1) 0.01 Sixth layer (ultraviolet absorbing layer) Gelatin 0.55 Ultraviolet absorbing agent (UV-1) 0.40 Color image stabilizer (Cpd-13) 0.15 Color image stabilizer (C d-6) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.15 Liquid paraffin 0.03 Color image stabilizer (Cpd-14) 0 .01

The compounds used here are shown below.

[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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In order to keep the film of the completed photosensitive material constant, the gelatin in each layer was added while changing the ratio with the oil-soluble component so as to be constant. Based on the photographic materials obtained as described above, photographic materials were prepared which differed only in that the emulsion in the red-sensitive layer and the cyan coupler were replaced as shown in Table 9, and these were used as samples 101 to 118. However, the fifth layer (red-sensitive emulsion layer) of the sample using the cyan couplers (10) and (11) had an emulsion coating amount of 0.17 g / m ² and a cyan coupler coating amount of 0.16 g / m ² . . In addition,
The coating amount of the fifth layer (red-sensitive emulsion layer) of the sample using the cyan coupler (20) was 0.12 g / m ² , and the coating amount of the cyan coupler was 0.16 g / m ² . Sample 113-1
Reference numeral 15 denotes the coating amount of the first layer including the coupler without changing the composition without replacing the yellow coupler (ExY) of the first layer (blue-sensitive emulsion layer) of Samples 107 to 109 with ExY-2 in an equimolar amount. Was reduced to 80% by weight. Similarly, samples 116 to 118 correspond to sample 110
Except that the yellow couplers in the first layer of Nos. -112 were replaced with ExY-3 in an equimolar amount, and the coating amount of the first layer including the coupler was reduced to 70% by weight without changing the composition. It is.

[0085]

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To examine the sensitivity change and gradation change corresponding to the degree of mixing of the bleach-fix solution in the developer of the 18 kinds of photosensitive materials thus obtained, exposure was performed for 1 second through an optical wedge and a red filter. About one hour later, the following processing steps and a color development processing using a processing solution were performed. The degree of mixing of the bleach-fix solution into the developer is 0 ml / liter,
0.2 ml / liter and 0.4 ml / liter. The reflection density of the processed sample thus prepared was measured to obtain a characteristic curve. Sensitivity is 0.5% above fog density
The reciprocal of the exposure required to give a high density
Sensitivity at 1 second exposure (degree of mixing of bleach-fixing solution; 0)
(ml / liter) as 100, and when the mixing degree of the bleach-fixing solution was 0 ml / liter, 0.2 ml / liter, and 0.4 ml / liter, they were expressed as Sa, Sb, and Sc, respectively. The gradation is represented by the difference between the density for the exposure amount that is increased by 0.5 in log E from the exposure amount for which the sensitivity was obtained, and the density for which the sensitivity was obtained. When expressed as liter and 0.4 ml / liter, they were expressed as γa, γb and γc, respectively. Exposure for Macbeth chart was also performed, and the sensitivity of blue and green was evaluated. The evaluation was expressed as Δ (poor), （(good), ◎ (excellent).

[0087]

[Table 9]

[0088]

[Table 10]

(Development) The exposed samples were subjected to color development in the following processing steps using a paper processor. A predetermined amount of the bleach-fixing solution was mixed into the developing solution by separate addition. Processing Step Temperature Time Color development 35 ° C 45 seconds Bleach-fix 30-35 ° C 45 seconds Rinse I 30-35 ° C 20 seconds Rinse J 30-35 ° C 20 seconds Rinse K 30-35 ° C 20 seconds Drying 70-80 ° C 60 seconds ( The composition of each processing liquid is as follows. Color developer Amount water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N -(Α-methanesulfonamidoethyl) -3- 3-methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g N, N-di (sulfoethyl) hydroxylamine · 1Na 0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Add water 1000 ml pH (25 ° C) 10.05

Bleach-fix solution Amount 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 1000 ml pH (25 ° C.) 6 2.0 Rinse liquid Ion exchange water (Calcium and magnesium are each 3 ppm or less)

From Table 10, the effect of the present invention is clear. That is, the sample 101 using the conventional cyan coupler
In the case of -103, the change in photographic performance with respect to the degree of mixing of the bleach-fix solution in the developer is small, but the color reproducibility of blue and green is not preferred. Sample 1 using the cyan coupler of the present invention
Indeed color reproducibility in 04-118 is preferred, the sample 10 to the red-sensitive layer emulsion was used R ₁ is sulfur alone sensitization
In 4, 107, 110, 113 and 116, the change in photographic performance with respect to the degree of mixing of the bleach-fix solution in the developer is a significant problem. However, the combination of the cyan coupler of the present invention and the emulsion subjected to gold sensitization can achieve both excellent color reproducibility and little change in photographic performance with respect to the degree of mixing of the bleach-fix solution in the developer, In addition, it was also found that the sample of this combination exhibited a smaller change in photographic performance with respect to the degree of mixing of the bleach-fix solution into the developer than the sample using ExC as the cyan coupler.

Example 2 Samples 201 to 201 in which the layer structure of Example 1 was changed as follows.
209 was manufactured and the same test as in Example 1 was performed. Was
However, for the samples using the cyan couplers (19) and (11),
The emulsion coating amount of the fifth layer (red-sensitive emulsion layer) is 0.17 g / m2.
^Two, Cyan coupler coating amount: 0.16 g / m ^TwoAnd

[0093]

[Table 11]

[0094]

[Table 12]

Paper support laminated on both sides with polyethylene
After subjecting the body surface to corona discharge treatment, dodecylbenze
Provide a gelatin undercoat layer containing sodium sulfonate,
Furthermore, various photographic constituent layers are applied, and the layer constitution shown below
Was produced (sample 201). Coating liquid
Was prepared as follows. Preparation of Coating Solution for Fifth Layer 35.0 g of cyan coupler (ExC), dodecylbenze
Sodium sulfonate 14.0 g, ethyl acetate 100
ml, color image stabilizer (Cpd-1) 43.8 g, color image stabilizer
3.3 g of the agent (Cpd-9), the color image stabilizer (Cpd-1)
8) 2.2 g, color image stabilizer (Cpd-19) 19.7
g, 5.5 g of color image stabilizer (Cpd-20), solvent (So
lv-10) was added and dissolved.
Emulsified and dispersed in 10% gelatin aqueous solution by high-speed stirring emulsifier
To prepare an emulsified dispersion. The obtained dispersion is
Mix and dissolve with silver chlorobromide emulsion prepared by the method shown,
A fifth layer coating solution was prepared to have the composition shown below.
The coating solution for the first to seventh layers is the same as the coating solution for the fifth layer
Prepared by the method. As the gelatin hardener for each layer, 1-O
Xy-3,5-dichloro-s-triazine sodium salt
Was used. Also, Cpd-15 and Cpd-16 are added to each layer.
The total amount of each is 25.0 mg / m ^TwoAnd 50.0mg / m
^TwoWas added so that

The silver chlorobromide emulsion of each photosensitive emulsion layer was subjected to spectral sensitization using the same compounds and the same amounts as used in Example 1. Further, the same dye as that used in Example 1 was added to the emulsion layer to prevent irradiation.

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). However, the silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper (Central surface average roughness SR _A =
0.12 μm) [The first layer contains polyethylene containing a white pigment (containing 14% by weight of TiO ₂ ) and a bluish dye (ultramarine)] First layer (blue-sensitive yellow coloring layer) Silver chlorobromide emulsion (implemented) 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-17) 0.19 Solvent (Solv-8) 0.18 Solvent (Solv) -1) 0.18 Color image stabilizer (Cpd-1) 0.06

Second layer (color mixture preventing layer) Gelatin 0.64 Color mixture inhibitor (Cpd-4) 0.10 Solvent (Solv-2) 0.16 Solvent (Solv-3) 0.08 Third layer (green light sensitive) Color magenta color developing layer) Silver chlorobromide emulsion (same as the emulsion of the third layer of Example 1 except that it is a 1: 3 mixture (silver mole ratio) of large size emulsion G1 and small size emulsion G2) 0. 14 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-6) 0.16 Color image stabilizer (Cpd-18) 0.02 colors Image stabilizer (Cpd-2) 0.02 Solvent (Solv-7) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.41 Ultraviolet absorbing agent (UV-3) 0.47 Color mixing inhibitor (Cpd-4) ) 0.05 Solvent (Solv-9) 0.24

Fifth layer (red-sensitive cyan coloring layer) Silver chlorobromide emulsion R ₁ 0.20 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-9) 0.03 colors Image stabilizer (Cpd-18) 0.02 Color image stabilizer (Cpd-19) 0.18 Color image stabilizer (Cpd-1) 0.40 Color image stabilizer (Cpd-20) 0.05 Solvent (Solv) -10) 0.14 Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-3) 0.16 Color mixing inhibitor (Cpd-4) 0.02 Solvent (Solv-9) 0.08 Seven layers (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

From the results shown in Table 12, it can be seen that even in this layer configuration, the same effect as in Example 1 was achieved by the combination of the cyan coupler of the present invention and the emulsion subjected to gold sensitization.

Example 3 Samples 301 to 109 differing from Samples 101 to 109 of Example 1 only in that all the gelatin in the light-sensitive material was replaced with gelatin α having a small calcium content.
Sample No. 09 was prepared, and the 18 types of samples were coated with the coating solution of the fifth layer (red-sensitive emulsion layer) immediately after the preparation of the coating solution x, and the sample y coated after the coating solution was prepared and aged at 40 ° C. for 2 hours. After preparing the coating solution for 8 hours at 40 ° C., the coated sample z was prepared for each sample, and the red-sensitive sensitivities Sx, Sy and Sz were determined in the same manner as in Example 1.
x-Sy (ΔS ₁ ) and Sx-Sz (ΔS ₂ ) were used as measures of the stability of the coating solution over time. In addition, the same test as in Example 1 was performed for the sample z applied after the aging at 40 ° C. for 8 hours after preparation of the coating solution. Gelatin α having a low calcium content was prepared by subjecting the gelatin used in Example 1 to lime treatment to remove calcium. When the total calcium content in the light-sensitive materials of Samples 301 to 309 prepared using this gelatin α was measured, it was 6.4 m
g / m ² . The total calcium content in the light-sensitive material using gelatin which has not been decalcified is 3
It was 0.5 mg / m ² .

[0106]

[Table 13]

[0107]

[Table 14]

From Tables 13 and 14, the effect of the present invention is clear. That is, Sample 3 using the cyan coupler of the present invention
Nos. 05 to 309 can reduce the degree of desensitization after aging of the coating solution and can overcome the instability of the production performance even when gelatin α having a small calcium content is used, and the color reproducibility is the same as in Examples 1 and 2 above. In addition to the above, it is possible to provide a light-sensitive material which is stable in photographic properties even when the composition of the processing solution is changed, and is excellent in running processing.

[0109]

According to the present invention, stable photographic properties are provided, which are excellent in rapid processing properties and color reproducibility, stable in photographic properties even when the composition of the processing solution changes, and have little change in sensitivity of the coating solution over time. Can be provided.

Claims (2)

(57) [Claims] To 1. A on a support, un dye-forming coupler-containing light-sensitive silver halide emulsion layer, a magenta dye-forming coupler-containing light-sensitive silver halide emulsion layer, the yellow dye-forming coupler-containing light-sensitive silver halide emulsion layer In a silver halide color photographic light-sensitive material having a photographic constituent layer comprising at least one layer and at least one non-light-sensitive colloid layer, a silver halide emulsion layer containing the cyan dye-forming coupler is represented by the following general formula (Ia): It is characterized by containing at least one of the pyrroloazole-type cyan dye-forming couplers represented and containing silver chlorobromide or silver chloride having a silver chloride content of 90 mol% or more chemically sensitized with a gold compound. Silver halide color photographic light-sensitive material. Embedded image (In the general formula (Ia), Za is -NH- or -CH
(R ₃ ) —, Zb and Zc each represent —C
(R ₄ ) = or -N =. R ₁ , R ₂ and R ₃
Represents 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 hydrogen atom or a substituent ( however, Za represents —NH—, Zb represents —N
= A, Zc is -C a (R ₄₎ =, to represent respectively
R ₄ represents an aliphatic group, an aryl group, an alkyl aryl
Or heterocyclic acyl group, alkyl / aryl or
Represents a heterocyclic oxycarbonyl group, a carbamoyl group, a sulf
An amoyl group, a hydroxy group, a cyano group or a nitro group
Represent. The alkyl and aryl groups contained in these groups are also
Or the heterocyclic group is further substituted with another substituent.
Is also good. ). 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. The group of R ₁ , R ₂ , R ₃ , R _4, or X becomes divalent and may form a homopolymer or a copolymer by bonding to a dimer or higher multimer or a polymer chain. . ) 2. The silver halide color photographic light-sensitive material 1 wherein the total content of calcium atoms contained in the photographic constituent layer is 1
^{2. The} silver halide color photographic light-sensitive material according to claim 1, wherein the amount is 15 mg or less per m < ² >.