JPH0521224B2 - - Google Patents

Description

Detailed Description of the Invention Background of the Invention [Technical Field] The present invention exhibits high sensitivity, high color development, good spectral absorption characteristics, and color development of couplers even when processed with a color developer from which benzyl alcohol has been removed. The present invention relates to a silver halide color photographic material that provides cyan dye images without deterioration in quality. [Prior art and its problems] Usually in silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced by an aromatic primary amine color developing agent, and at this time, the color developing agent produced is A dye image can be obtained by coupling the oxidized form of the main drug with couplers that form yellow, magenta, and cyan dyes. Couplers widely used to form the cyan dyes are phenolic or naphtholic cyan couplers. Due to the recent rise in the price of silver, the manufacturing cost of silver halide color photographic materials has increased, and for this reason, there is a strong need for the development of couplers that require a small amount of silver, that is, can save silver. . Furthermore, the development of techniques for increasing the reactivity of couplers is a constant challenge for those skilled in the art. That is,
It is already well known that there is a difference in the density of dyes obtained when processing with a fixed amount of silver and a fixed molar amount of coupler, but it is known that the worse the color development, the more unreacted residual coupler there is. It means.
That is, when setting a silver halide photographic light-sensitive material for the purpose of obtaining a dye of a certain density, the molar concentration of the coupler must be increased or the amount of silver used must be increased. . This means an increase in the manufacturing cost of silver halide color photographic materials. It has been found that certain unreacted residual couplers have drawbacks such as poor storage stability of the dye produced. Many proposals have been made to improve the color forming properties of these couplers. One such proposal is
Examples include the use of two-equivalent couplers, that is, couplers that require only two exposed silver halide molecules to obtain one molecule of dye;
No. 36894, JP-A-47-21139, JP-A No. 56-65134,
It is described in No. 50-117422, No. 55-32071, No. 56-1938, etc. Another proposal is to use a coupler with a hydrophilic group introduced, for example, JP-A-53-109630 and JP-A-55-
No. 163537, No. 56-29235, No. 56-99341, No. 57
−136649, No. 57-155538, No. 56-80045,
No. 58-42045 etc. are mentioned. however,
The couplers obtained using these methods had insufficient coloring performance. Furthermore, JP-A-59-102234
In this issue, a method is described in which a 2,5-diacylaminophenol uncoupler and an alkyl-substituted phenol compound are used in the same oil agent. Although this method does improve color reproducibility,
It was unsatisfactory in terms of color development. For this reason, generally, benzyl alcohol is added to obtain a sufficient coloring property in a cyclic form. However, from the viewpoint of depollution, the removal of benzyl alcohol added to the coloring liquid has been taken up as a major problem. The decrease in color development due to the removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for the emergence of phenolic cyan couplers in which benzyl alcohol has at least high color development. In addition, the maximum absorption wavelength of the dyes produced by many conventionally known cyan couplers is
Many have a wavelength in the range of 630nm to 690nm. However, the preferred maximum absorption wavelength for color reproduction is
The wavelength range is from 645nm to 665nm, and wavelengths shorter than 645nm produce cyan pigments with a bluish tint, impairing the reproducibility of the green color seen in bamboo and tree leaves, and causing maximum absorption wavelengths above 665nm. This pigment is a cyan pigment with a greenish tint, which has the disadvantage of impairing the reproducibility of blue colors seen in the sky and the sea.Therefore, there is a need for a cyan coupler with a maximum absorption wavelength that is favorable for color reproduction. It had been. [Object of the Invention] The first object of the present invention is to provide a silver halide color photographic light-sensitive material having a cyan image that is highly sensitive and provides high color density. A second object of the present invention is to provide a silver halide color photographic light-sensitive material that provides a cyan dye image that does not cause a decrease in color development even when processed with a color development liquid from which benzyl alcohol has been removed. A third object of the present invention is to provide a silver halide color photographic material that provides a cyan image with less unreacted residual coupler. A fourth object of the present invention is that it can be manufactured relatively inexpensively,
Another object of the present invention is to provide a silver halide color photographic material that provides cyan images that can save silver. A fifth object of the present invention is to provide a silver halide color photographic material that has good spectral absorption characteristics, excellent color reproducibility, and can provide cyan dye images. The above object of the present invention is achieved by using a silver halide color photographic light-sensitive material containing a photographic cyan coupler represented by the following general formula [] and a phenol derivative represented by the following general formula [] in a photographic constituent layer. It was done. General formula [] [In the formula, R ₁ represents a hydrogen atom or a halogen atom, R ₂ represents an alkyl group or an acylamino group, R ₃ represents an aryl group, and Z represents a hydrogen atom or a coupling with an oxidation product of a color developing agent. Represents a group that can be eliminated during a reaction. ] General formula [] [In the formula, R ₄ represents an alkyl group, aryl group, alkoxy group, or amino group, R ₅ represents a monovalent group, n represents an integer from 0 to 3, and when n is 2 or more, R ₅ is , may be the same or different. ] R ₁ in the general formula [] is a hydrogen atom or a halogen atom (chloro atom, bromine atom, fluorine atom, etc.)
, R ₂ represents an alkyl group or an acylamino group, and the alkyl group is an alkyl group having 1 to 20 carbon atoms, preferably an unsubstituted alkyl group having 1 to 5 carbon atoms. The acylamino group represents an alkylcarboxamide group or an arylcarboxamide group, and the alkylcarboxamide group is a straight-chain or branched alkyl group having 1 to 20 carbon atoms, and this alkyl group has no substituent. may have. Preferred substituents include a halogen atom, a phenyl atom, a phenoxy group, a phenylthio group, an alkylsulfonyl group having 1 to 20 carbon atoms, a phenylsulfonyl group, and the like. The phenyl group may be substituted with a monovalent group,
Examples of monovalent groups include halogen atoms (chloro atom, bromine atom, fluorine atom, etc.), alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and halogen atoms having 2 to 20 carbon atoms. Alkenyloxy group, alkoxycarbonyl group having 1 to 20 carbon atoms, phenoxycarbonyl group, having 1 carbon atom
to 20 alkylsulfonamide groups, phenylsulfonylamide groups, alkyl or dialkylaminosulfonyl groups having 1 to 20 carbon atoms, phenylaminosulfonyl groups, alkyl or dialkylaminocarbonyl groups having 1 to 20 carbon atoms, cyano groups , nitro group, hydroxy group, carboxy group, alkylsulfonyl group having 1 to 20 carbon atoms, phenylsulfonyl group, etc. The alkyl group and phenyl group may be further substituted with the above monovalent group. The arylcarboxamide group represents a phenylcarboxamide group, and the phenyl group may have the above-mentioned monovalent group. R ₃ represents an aryl group, and the aryl group represents a phenyl group, and the phenyl group may have the above-mentioned monovalent group. The cyan coupler represented by the general formula [] of the present invention is more preferably represented by the following general formulas [] and []. General formula [] [In the formula, R ₆ represents an alkyl group, Z ₁ has the same meaning as Z in the general formula [], and represents a hydrogen atom or an eliminable group, and R ₇ represents a hydrogen atom or a group capable of leaving the coupler. represents a group (hereinafter referred to as a ballast group). ] General formula [] [In the formula, R ₈ represents a monovalent group, R ₉ has the same meaning as R ₇ in the general formula [] and represents a ballast group, Z ₂ has the same meaning as Z in the general formula [], and represents a hydrogen atom or an elimination group. represents a possible group, m represents an integer from 0 to 5, m
is 2 or more, R ₈ may be the same or different. ] In the present invention, R ₆ represented by the general formula [] is,
It represents an alkyl group, preferably a straight chain or branched alkyl group having 1 to 8 carbon atoms, for example,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group,
Examples include a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and an ethyl group is particularly preferred. This alkyl group may have a substituent. In the present invention, R ₈ represented by the general formula [ ] is
It represents a monovalent group, and examples of monovalent groups include halogen atoms (chloro atom, fluorine atom, etc.), alkyl groups (methyl group, trifluoromethyl group,
tert-butyl group, etc.), alkoxy group (ethoxy group,
1,1,2,3,3,3-hexafluoropropyloxy group, 1,1,2-trifluoro-2-chloroethoxy group, etc.), alkenyloxy group (perfluoropropenyl group, etc.), ester group (ethoxy carbonyl group, phenoxycarbonyl group, etc.),
Sulfonamide group (methanesulfonamide group, ethasulfonamide group, dimethylaminosulfonamide group, benzenesulfonamide group, toluenesulfonamide group, etc.), sulfamoyl group (N, N
-dimethylsulfamoyl group, butylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (N,N-dimethylcarbamoyl group, butylcarbamoyl group, phenylcarbamoyl group, etc.), cyano group, nitro group, etc. , preferably a halogen atom or a sulfonamide group. Particularly preferred is a fluorine atom. In the present invention, R ₇ or R ₉ represented by the general formula [] or [] represents a ballast group, and the ballast group is preferably a group represented by the following general formula []. General formula [] [In the formula, Y represents a divalent bonding group of -O-, -S-, _-SO2- , and _R10 preferably has a carbon number of 1 to
20 alkylene groups (e.g. methylene, 1,1-
Ethylene, 1,1-propylene, 1,3-propylene, 2-methyl-1,1-propylene, 1,1
-pentylene, 1,1-heptylene, 1,1-nonylene, 1,1-undecylene, 1,1-tridecylene, 1,1-pentadecylene, etc.), and R ₁₁ represents a monovalent group; Examples of such groups include halogen atoms (chlorine atoms, fluorine atoms, etc.), hydroxy groups, alkyl groups having 1 to 20 carbon atoms (for example, methyl groups, ethyl groups, tert.
-butyl group, tert-pentyl group, tert-octyl group, pentadecyl group, etc.), cycloalkyl group (e.g., cyclopentyl group, etc.), alkoxy group (methoxy group, ethoxy group, isopropoxy group, butoxy group, hexyloxy group, dodecyloxy group, etc.), alkylsulfonamide group (methanesulfonamide group, ethanesulfonamide group, butanesulfonamide group, octylsulfonamide group, hexadecylsulfonamide group, etc.), arylsulfonamide group, (benzenesulfonamide group, m
-chlorobenzenesulfonamide group, toluenesulfonamide group, p-methoxybenzenesulfonamide group, p-dodecyloxybenzenesulfonamide group, etc.), aminosulfonamide group (N, N
-dimethylaminosulfonamide group, N-methyl-N-butylaminosulfonamide group, etc.), alkylsulfamoyl group (butylsulfamoyl group, tert-butylsulfamoyl group, dodecylsulfamoyl group, etc.), aryl Sulfamoyl groups (benzenesulfamoyl group, toluenesulfamoyl group, dodecyloxybenzenesulfamoyl group, etc.), alkylsulfonyl groups (methanesulfonyl group, butanesulfonyl group, etc.), arylsulfonyl groups (benzenesulfonyl group, p -benzyloxyphenylfonyl group, p-hydroxyphenylsulfonyl group, etc.) or alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, hexadecyloxycarbonyl group, etc.). l represents an integer from 1 to 4, preferably 1 or 2. When l is 2 or more,
R ₁₁ may be the same or different. In the present invention, Z, Z ₁ and Z ₂ represented by the general formula [], [] or [] are each a hydrogen atom or a hydrogen atom that can be eliminated during a coupling reaction with an oxidation product of a color developing agent. such groups are well known to those skilled in the art. These groups can also control the reactivity of the coupler and, after leaving the coupler, perform functions such as development inhibition, bleach inhibition, bleach acceleration, color correction, etc. layers can be advantageously influenced. Typical examples of these groups include halogen atoms (chloro atom, fluorine atom, etc.), alkoxy groups (methoxyethylaminocarbonylmethoxy group, methanesulfonylethoxy group, etc.), aryloxy groups (p-ethoxycarbonylphenoxy group, p-methoxyphenoxy group, p-butanesulfonamide phenoxy group, p-β-carboxypropanamide phenoxy group, etc.), arylthio group (o-butoxyphenylthio group, p-tert-butylphenyl ruthio group, m-butanesulfonamidophenylthio group, etc.). Groups that are eliminated during such coupling are described, for example, in U.S. Pat. No. 2,455,169;
Same No. 3227551, No. 3432521, No. 3476563, Same No.
No. 3617291, No. 3880661, No. 4052212 and No.
No. 4134766 and UK Patent and Published Patent Application No.
No. 1466728, No. 1531927, No. 1533039, No.
2006755A and 2017704. Next, the phenol derivative represented by the general formula [] of the present invention (hereinafter referred to as the phenol derivative of the present invention) will be described. The alkyl group represented by R ₄ in the general formula [] is a linear or branched alkyl group having 1 to 20 carbon atoms, and this alkyl group may have a substituent. Such alkyl groups include (for example, methyl group, ethyl group, butyl group, tert-butyl group, hexyl group, octyl group,
Examples include dodecyl group, benzyl group, dodecyloxycarbonylmethyl group, and the like. The aryl group represented by R ₄ is preferably a phenyl group, and this aryl group may have a substituent. Examples of the phenyl group having a substituent include methoxyphenyl, tert-butoxyphenyl , benzyloxyphenyl, cyclohexyloxyphenyl, dodecyloxyphenyl, dodecyloxycarbonylphenyl, butanesulfonamidophenyl, hexadecylsuccinimidophenyl, pivaloylamidophenyl, and the like.
The alkoxy group represented by R ₄ is an alkyloxy group having 1 to 20 carbon atoms, for example, tert-
Examples include butoxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, and the like.
The amino group of R ₄ represents an alkylamino group or an arylamino group, and the alkylamino group is
(For example, butylamino group, N-methyl-N-dodecylamino group, tetradecylamino group, N-benzyl-N-hexylamino group, N,N-dibenzylamino group, N,N-di-(2- (ethylhexyl) amino group, etc.), arylamino group,
(Dodecyloxyphenylamino group, N-methyl-N-tetradecyloxyphenylamino group, N
-β-methanesulfonamidoethyl-N-dodecyloxyphenylamino group, lauroylamidephenylamino group, dodecyloxycarbonylphenylamino group, etc.). In the present invention, represented by the general formula []
R ₅ represents a monovalent group, and the general formula []
It has the same meaning as R ₈ represented by R 8 and R ₁₁ represented by the above general formula [ ]. n represents an integer from 0 to 3, preferably 0 or 1. Also R ₄
is particularly preferably a substituted phenyl group. Typical specific examples of the cyan coupler of the present invention are described below, but the present invention is not limited thereto.

【table】

【table】

[Table] Representative examples of the phenol derivatives of the present invention are described below, but the present invention is not limited thereto. The cyan coupler of the present invention can be easily synthesized by conventionally known means. General synthesis examples are shown below. Synthesis example 1 (synthesis of coupler No. 21) 2-pentafluorobenzamide-4-chloro-5-aminophenol 35.3g, pyridine 9.5g
was added to 3500c.c. of acetonitrile and stirred at room temperature.
38.8 g of -(2,4-di-tert-amyl)phenoxyisopentanoyl chloride was slowly added dropwise. After the dropwise addition was completed, the mixture was further stirred at the same temperature for 30 minutes, and then the reaction solution was added to water. The resulting oil was extracted using ethyl acetate, washed with water, the ethyl acetate was separated and concentrated under reduced pressure. The residue was purified using silica gel column chromatography. Crystallization from acetonitrile yielded 25.4 g of white crystals. The structure was determined using NMR and MASS. The phenol derivative of the present invention can be easily synthesized by conventionally known methods. General synthesis examples are shown below. Synthesis example 2 (synthesis of p 8) 50g (0.2mol) bisphenol S, 30g
(0.22 mol) of potassium carbonate was added to 400 ml of water,
The mixture was heated to 70° C. and stirred, and 50 g (0.22 mol) of dodecyl bromide was added dropwise little by little. After dropping, add 2 more
The mixture was heated and stirred at the same temperature for a period of time. The reaction solution was allowed to cool to air temperature, extracted with ethyl acetate, washed with 1N-K ₂ CO ₃ aqueous solution, separated the oil layer, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure.
N-hexane was added to the residue for crystallization. 35.4g
(45% yield) of white crystals were obtained. The structure was determined using NMR and MASS. The cyan dye-forming couplers and phenolic derivatives used in this invention can be used in conventional methods and purposes for using cyan dye-forming couplers in photographic technology. Typically, the cyan coupler and phenol derivative of the present invention are used by being contained in a photographic constituent layer of a silver halide emulsion layer and/or a non-light-sensitive layer adjacent thereto. A silver halide color photographic light-sensitive material can be obtained by blending the cyan coupler and the phenol derivative into a silver halide emulsion and coating this emulsion on a support. This silver halide color photographic light-sensitive material may be monochromatic or multicolored. In the case of multicolor, the cyan coupler of the present invention is usually contained in a red-sensitive emulsion layer, but it may also be contained in a non-sensitized emulsion layer or an emulsion layer sensitive to the three primary color regions of the spectrum other than red. Each structural unit forming a dye image in the present invention consists of a single emulsion layer or multiple emulsion layers sensitive to a certain region of the spectrum. The photographic constituent layers necessary for the silver halide color photographic light-sensitive material, including the layers of image-forming units described above, can be arranged in various orders as known in the art. A typical multicolor silver halide color photographic light-sensitive material consists of a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler. a magenta dye image-forming unit consisting of at least one green-sensitive silver halide emulsion layer containing at least one magenta dye-forming coupler (at least one of which is a cyan coupler of the invention); and at least one yellow dye. It consists of a support carrying a yellow dye image-forming unit consisting of at least one blue-sensitive silver halide emulsion layer containing a forming coupler. This photographic light-sensitive material may have non-photosensitive layers, such as photographic constituent layers such as filter layers, intermediate layers, and subbing layers. In order to prepare a multicolor silver halide color photographic light-sensitive material using the coupler of the present invention, each light-sensitive layer containing a yellow dye-forming coupler and a magenta dye-forming coupler is also required. Yellow dye-forming couplers that can be used in the present invention include conventionally known ones. For example, the following general formula [] is used. General formula [] [In the formula, R ₁₂ is an alkyl group or an aryl group,
R ₁₃ represents an aryl group, and Z ₃ represents a group capable of being eliminated by coupling with an oxidation product of a color developing agent. ] The alkyl group represented by R ₁₂ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
Examples include iso-propyl group, tert-butyl group, and tert-octyl group. Particularly preferred is tet-butyl group. This alkyl group can have a substituent. Furthermore, the aryl group represented by R ₁₂ and R ₁₃ is
Preferably it is a phenyl group, and this phenyl group can have a substituent. Examples of substituents for this phenyl group include a halogen atom, an alkoxy group, an acylamino group, a sulfonamide group, and an alkoxycarbonyl group. In the general formula [], the group represented by Z ₃ that can be eliminated by coupling with the oxidation product of the color developing agent is preferably represented by the following general formula [] or []. General formula [] In the formula, B represents a nonmetallic atom group necessary to form a 5- or 6-membered ring, and examples of such nonmetallic atom groups include carbonate atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. be able to. Among these, carbon atoms and nitrogen atoms are preferred. Examples of the 5- or 6-membered heterocycle formed by B in the general formula [] include oxazolidinedione, thiazolidinedione, hydantoin, urazole, imidazole, and triazole. Preferred among these are hydantoin and urazole. General formula [] -O-R ₁₄ In the formula, R ₁₄ represents an aryl group, preferably a substituted aryl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, a carboxy group, an ester group, a sulfonamide group, an acylamino group, and a sulfonyl group. As magenta dye-forming couplers that can be used in the present invention, conventionally known ones can be mentioned. For example, the following general formulas "", [ ], or "XI". General formula [] [In the formula, R ₁₅ is an alkylcarbonyl group, arylcarbonyl group, or aryl group, R ₁₆ is a monovalent group, and Z ₄ is a hydrogen atom or a group that can be eliminated by coupling with an oxidation product of a color developing agent. represents. ] General formula [X] [In the formula, R ₁₇ is an alkyl group or an aryl group,
R ₁₈ represents an alkyl group, aryl group, or alkylthio group, and Z ₅ represents a group capable of being eliminated by coupling with an oxidation product of a color developing agent. ] General formula [XI] [In the formula, R ₁₉ is a monovalent group, R ₂₀ is an alkyl group,
Aryl group, acylamino group, alkoxy group,
Z ₆ represents a hydrogen atom or a group capable of being eliminated by coupling with an oxidation product of a color developing agent. ] Further, the cyan dye-forming coupler of the present invention can be further combined with other cyan dye-forming couplers. The yellow and magenta couplers represented by the general formulas [], [], [] and [XI] are:
Specifically, the following compounds may be mentioned, but the compound is not limited thereto. Further, each of these couplers may be arbitrarily selected as required, and two or more types may be used in combination. The cyan coupler of the present invention, the phenol derivative, and each of the above-mentioned couplers of the present invention may be incorporated into a silver halide light-sensitive material by a conventionally known method. For example, the cyan coupler and phenol derivative of the present invention, or each coupler described above, is dissolved in a mixture of a known high boiling point solvent and a low boiling point solvent such as butyl acetate or butyl propionate, and then mixed with an aqueous gelatin solution containing a surfactant. death,
Next, after emulsifying with a high-speed rotary mixer, a colloid mill, or an ultrasonic disperser, it can be added to silver halide to prepare the silver halide emulsion used in the present invention. As the high boiling point solvent that can be used, conventionally known ones can be mentioned. For example, the following general formula [XII],
Things like [], [] and []. Among them, general formulas [XII] and [ ] are preferred
Among these, phthalic acid diester is particularly preferred. General formula [XII] [In the formula, B ₁ is a halogen atom, carbon number 1 to 20
represents an alkoxy group, _-COOR21 , _R21 represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and p represents an integer of 0 to 3. When p is 2 or more, B ₁ may be the same or different. ] General formula [] O=P(-OR ₂₁ ) ₃ [wherein R ₂₁ is represented by the above general formula []
Synonymous with R ₂₁ . ] General formula [] [In the formula, R ₂₂ and R ₂₃ each represent an alkyl group or a phenyl group having 1 to 20 carbon atoms, and R ₂₄
represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group. Also, R ₂₃ and R ₂₄ are
A 5- or 6-membered ring may be formed using a group of nonmetallic atoms. ] General formula [XV] R ₂₅ COOR ₂₁ [In the formula, R ₂₅ represents an alkyl group having 1 to 20 carbon atoms, and R ₂₁ is R ₂₁ represented by the above general formula [ ]
is synonymous with ] The above general formulas [], [], [] and [
] Specific examples of the high boiling point solvent represented by the formula include the following compounds, but the high boiling point solvent of the present invention is not limited thereto.
Moreover, these high boiling point solvents may be selected arbitrarily, and two or more types may be used in combination. HBS−21 O=P(−OC ₄ H ₉ ) ₃ HBS−24 O=P(−OC ₆ H ₁₃ ) ₃ HBS−43 CH ₃ COOC ₁₂ H ₂₅ HBS−46 CH ₁₁ H ₂₃ COOC ₂ H ₅ HBS−51 CH ₃ COOCH ₂ CH ₂ OCH ₂ CH ₂ OC ₄ H ₉ The silver halide color photographic light-sensitive material prepared according to the present invention usually contains a colored coupler for color correction, a colorless coupler for improving the hue of the light-sensitive material, or an ultraviolet absorber, if necessary. Various additives may be used. Colored couplers that can be used include colored magenta couplers and colored cyan couplers, which are represented by the following general formulas [] and []. General formula [] M-N=N-Ar [wherein M represents a residue obtained by removing one hydrogen atom from the active site of the magenta coupler, and Ar represents an aryl group. ] The magenta coupler residue represented by M is preferably represented by the general formula [ ]. General formula [] C(-J _q --N=N-Ar [wherein, C is the residue of the phenol-based or naphthol-based cyan coupler excluding the active site hydrogen, J is the divalent bonding group, Ar represents an aryl group, and q represents 0 or 1, respectively.] The cyan coupler residue represented by C is preferably represented by the following general formula []: General formula [] In the formula, R ₂₆ represents an alkyl group or an aryl group. The colored magenta couplers and colored cyan couplers represented by the general formulas [] and [] include the following compounds, but are not limited to these, and two or more of each may be used in combination. DIR couplers that can be used are represented by the following general formula [ ]. General formula [] Cp-(J')r-I In the formula, Cp represents a residue having a site capable of coupling with an oxidized color-forming ring imaging agent and having one hydrogen atom removed from that site. This Cp is preferably a cyan, yellow, or magenta coupler residue represented by the general formulas [], [], [], [], and [XI] (J' is Z, Z ₁ , Z ₃ , Z ₄ , Z ₅ , Z ₆
). J′ is released from Cp by reaction with the oxidation product of the color-forming ring imager,
Represents a divalent group capable of releasing by intramolecular nucleophilic substitution reaction, electron transfer, hydrolysis, etc.
represents an image-suppressing group. r represents an integer of 0 or 1. Further, as groups having other coupling-capable moieties and having one hydrogen atom removed from the moiety, the following general formulas [], [XI], [
]. General formula [] In the formula, examples of R ₂₇ include a halogen atom, an alkyl group, a cyano group, a nitro group, an alkoxy group, an acylamino group, a sulfonamide group, an ester group, a sulfamoyl group, a carbamoyl group, and a sulfonyl group. s represents an integer from 0 to 3, and when s is 2 or more, R ₂₇ may be the same or different. R ₂₈ represents a hydrogen atom, a halogen atom, an alkyl group, a cyano group, a nitro group, or the like. General formula [XI] In the formula, R ₂₉ , R ₃₀ and s have the same meanings as R ₂₇ , R ₂₈ and s shown in the above general formula [], respectively. General formula [XII] In the formula, R ₂₉ , R ₂₉ ′, s, and s′ have the same meanings as R ₂₉ and s shown in the general formula [], respectively. J′ in the general formula [] represents a divalent group,
It is preferably represented by the following general formula []. General formula [] -Y(-Ja _t -- In the formula, Y represents -O- or -S-, Ja represents an alkylene group, an arylene group, an arylene group, an ester group, or a divalent heterocyclic group, and t represents an integer from 1 to 3, and when t is 2 or more, Ja may be the same or different. The group represented by the general formula [] represents a development-inhibiting group, preferably mercapto. compounds, benztriazole compounds, etc. The DIR compound represented by the general formula [] is preferably represented by the following general formula []: General formula [] Cp[-Y(-J _a )-- _t ] _u ---I In the formula, Cp is the general formula [], [], [],
Y and Ja are cyan, yellow and magenta coupler residues represented by [] and [], and each group represented by the general formulas [], [XI] and [XII], respectively, and Y and Ja are represented by the general formula [], has the same meaning as Y and Ja represented by ], represents a development inhibiting group, t represents an integer of 1 to 3, and u represents an integer of 0 or 1, respectively. Examples of preferred DIR couplers are shown below, but the invention is not limited to these. Each DIR coupler can be selected depending on the purpose and use, and two or more types may be used in combination if necessary. Further, usable ultraviolet absorbers are represented by the following general formulas [] and []. General formula [] In the formula, R ₃₁ is an alkyl group having 1 to 20 carbon atoms,
R ₃₂ represents a halogen atom, v represents an integer of 1 or 2, and w represents an integer of 0 or 1, respectively. v
is 2, R ₃₁ may be the same or different. General formula [] In the formula, R ₃₃ is an aryl group or a vinyl group, R ₃₄
and R ₃₅ each represent a cyano group, an alkoxycarbonyl group or an arylsulfonyl group. Specific examples of the ultraviolet absorber used in the silver halide color photographic material of the present invention are listed below, but the invention is not limited thereto.
Moreover, two or more types may be used in combination if necessary. Stabilizers that can be used in the present invention include antifoggants and image dye stabilizers.
These are represented by the following general formulas [], [] and []. General formula [] In the formula, R ₃₆ , R ₃₇ and R ₃₈ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a sulfoxy group, and y represents an integer of 1 or 2. When y is 2, R ₃₈ may be the same or different, and
R ₃₇ and R ₃₈ may form a 5- or 6-membered ring using a nonmetallic atomic group. General formula [] In the formula, R ₃₆ , R ₃₇ and R ₃₈ are represented by the general formula [
] is the same as R ₃₆ , R ₃₇ and R ₃₈ . y′ represents an integer of 1 or 2, but when y′ is 2, R ₃₈ may be the same or different,
R ₃₈ may form a 5- or 6-membered ring at the ortho position. General formula [] In the formula, R ₃₉ represents a phenoxycarbonyl group, a benzenesulfonamide group, or an alkylsulfonamide group, a represents an integer from 1 to 3, and when a is 2 or more, R ₃₉ may be the same or different. You can leave it there. Below are the general formulas [], [] and [
] Specific examples of stabilizers represented by the following are shown below, but the present invention is not limited thereto, and two or more kinds may be used in combination as necessary. The cyan coupler and phenol derivative of the present invention may be separately dispersed and each added to the same silver halide emulsion, but it is preferable to dissolve and add both at the same time. When the cyan coupler of the present invention is added to a silver halide emulsion,
It is usually added in an amount of about 0.01 to 2 mol, preferably 0.03 to 0.5 mol, per mol of silver halide. The effect of the present invention will be more pronounced as the amount of the phenol derivative of the present invention is added to the cyan coupler of the present invention, but specifically, 0.1 to 10 g, preferably 0.25 to It is added in a range of 3g. Further, in the present invention, the object of the present invention can be achieved even when used in combination with various conventionally known additives. However, by combining more preferable combinations, the objects of the present invention can be achieved to a higher level, and even other effects can be added. That is, by using the DIR coupler, it was possible to improve the graininess. The effects of the present invention could be enhanced by a preferable combination with a high boiling point solvent. By combining with a stabilizer (particularly an antifoggant), it was possible to suppress fog caused by color development. Furthermore, by combining it with a stabilizer (for example, an ultraviolet absorber), it was possible to improve the light resistance of the dye produced by color development. From this, it will be fully understood that two or more of these or other additives may be used in combination depending on the purpose. The amount of DIR coupler that can be used is preferably in the range of 0.001 to 2.0 mol % per mol of silver halide. In the sensitive layer, the content is in the range of 0.001 to 1.0 mol%, particularly preferably 0.01 to 0.8 mol%. In the low sensitivity layer
The range is from 0.05 to 2.0 mol%, particularly preferably
It is 0.1-1.5 mol%. The amount of the high boiling point solvent that can be used is preferably in the range of 1 to 300 wt% based on the coupler weight, particularly preferably 30 to 300 wt%.
It is 150wt%. Stabilizers (e.g. antifoggants) that can be used include:
It can be added to any photosensitive layer or intermediate layer, and the amount of the antifoggant added to each layer is preferably in the range of 0.001 to 0.5 g/m ² per unit m ² , particularly Preferably 0.005~
It is 0.1g/ ^m2 . The usable ultraviolet absorber is preferably used in the intermediate layer, particularly preferably in the intermediate layer furthest from the support. This UV absorber is
It is preferably used in a range of 0.001 to 0.5 g/m ² per unit m ² , particularly preferably 0.005 to 0.1
g/ ^m2 . The silver halide used in the silver halide emulsion used in the present invention may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used. The silver halide emulsion constituting the silver halide emulsion layer according to the present invention can be produced by a conventional manufacturing method,
Various manufacturing methods, such as those described in Japanese Patent Publication No. 46-7772, can be used to form an emulsion of silver salt grains consisting of at least a portion of a silver salt whose solubility is greater than that of silver bromide, and then to form an emulsion of silver salt grains consisting of at least a portion of a silver salt having a solubility greater than that of silver bromide; such as converting at least a part of the into silver bromide or silver iodobromide,
Manufacturing method of so-called conversion emulsion, or 0.1μm
It can be produced by any production method such as the Lipman emulsion production method consisting of fine-grained silver halide having the following average grain size. Furthermore, the silver halide emulsions of the present invention may contain sulfur sensitizers such as arylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts, polyamines, etc. etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate,
2-Aurosulfobenzthiazole methyl chloride, etc., or, for example, ruthenium, rhodium,
Chemical sensitization can be carried out using water-soluble salt sensitizers such as iridium, specifically ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadite, alone or in combination as appropriate. Furthermore, the silver halide emulsion used in the present invention is
Various known photographic additives can be included. For example, “Research Disclosure”
A photographic additive as described in No. 17643, December 1978. The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. Various types of spectral sensitizing dyes are used, and these include 1
One species or two or more species can be used in combination. Spectral sensitizing dyes advantageously used in the present invention include, for example, US Pat.
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in No. 2442710, No. 2454620, and No. 2776280. The support according to the present invention may be appropriately selected from conventionally known supports such as plastic film, plastic laminate paper, baryta paper, and synthetic paper depending on the intended use of the photographic material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer. After the thus constructed silver halide color photographic material of the present invention is exposed, various photographic processing methods are used for color development processing. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component. Specific examples of this color developing agent include those based on p-phenylenediamine, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. Nylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-β-hydroxylethylamino)-toluene, 2-amino-5-(N
-ethyl-N-β-methanesulfonamidoethyl)aminotoluene sulfate, 2-amino-5-
(N-ethyl-N-β-methanesulfonamidoethylamino)toluene, 4-(N-ethyl-N-
β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-β-methoxyethyl)
Examples include aminotoluene. Among these, 2-amino-5 is particularly preferably used as a color developing agent when processing the photographic material of the present invention.
-(N-ethyl-N-β-hydroxyethylamino)-toluene, 2-amino-5-(N-ethyl-
N-β-methanesulfonamidoethylamino)-
It is selected from toluene. These color developing agents can be used alone or in combination of two or more,
Further, if necessary, it may be used in combination with a black and white developing agent such as hydroquinone. Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as an alkali metal halide such as potassium bromide, or a development regulator, For example, it may contain citradinic acid. The silver halide color photographic material of the present invention includes:
The above color developing agent is contained in the hydrophilic colloid layer,
It may be contained as the color developing agent itself or as its precursor. The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. The precursors of these aromatic primary amine color developing agents are:
For example, US Patent No. 3342599, US Patent No. 2507114, US Patent No.
No. 2695234, No. 3719492, British Patent No. 803783, Japanese Patent Application Publication No. 53-135628, No. 54-79035, Research
Disclosure Magazine No. 15159, No. 12146, No.
Described in No. 13924. These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during development. This amount varies depending on the type of photosensitive material, etc., but
Generally, the amount used is between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the above compound into a photographic light-sensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can also be added as an emulsified dispersion using a high-boiling organic solvent,
They can also be added by impregnation into latex polymers as described in US Pat. No. 14,850. The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development.
Many compounds are used as bleaching agents, but
Among them, polyvalent metal compounds such as (), cobalt (), and tin (), especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid Aminopolycarboxylic acids such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, metal complex salts, ferricyanates, dichromates, etc. are used alone or in appropriate combinations. Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 0.03 mol of each cyan coupler of the present invention as shown in Table 1 was weighed, added to a mixed solution of the same weight of dibutyl phthalate and three times the amount of ethyl acetate, and heated at 60°C. The solution completely dissolved by heating to 0.03% and the cyan coupler of the present invention
weighed mole by mole, and added dibutyl phthalate in the same weight as that weight into a mixed solution of the same weight of the phenol derivative of the present invention and three times the amount of ethyl acetate,
A solution completely dissolved by heating to 60°C, and 0.03 mole of each of the cyan couplers of the present invention were weighed, and the same weight of dibutyl phthalate and the same weight of a phenol compound other than the present invention were added. and 3 times the amount of ethyl acetate, and heated to 60°C to completely dissolve the solution. 10 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont) and 5% gelatin, respectively. The mixture was mixed with 4000 ml of an aqueous solution and dispersed using a colloid mill to obtain each emulsion. Next, these coupler dispersions were added to 500 g of silver chlorobromide emulsion containing 0.1 mole of silver (20 mole percent silver bromide), and 1,2-bis(vinylsulfonyl)ethane was added as a hardener. % solution (water:methanol=1:1) was added and applied to a subbed polyethylene-coated paper support, and dried to obtain a sample with a stable coating film. (Coated silver amount 7mg/100
^m2 ) These samples were subjected to wedge exposure according to a conventional method, and then subjected to the following processing. However, in the color development process, benzyl alcohol is added [color developer - (1)], and without it [color developer - (2)]
Two types of compositions were investigated. [Processing process] (30°C) Processing time Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes The composition of each processing solution in the processing process is as follows. [Color developer composition-(1)] 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl) aniline sulfate 5.0g Benzine alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1 and hydroxide Adjust the pH to 10.3 using sodium. 4-amino-3-methyl-N-ethyl-N-(β
-methanesulfonamidoethyl)aniline sulfate
5.0g Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Sodium bromide 1.4g Potassium bromide 0.5g Borax 39.1g Add water to make 1, and use sodium hydroxide.
Adjust to PH10.3. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 50g Ammonium sulfite (40% solution) 50ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28% solution) 20ml Ethylenediaminetetraacetic acid 4g Add water to make 1. Photographic properties were measured for each of the obtained samples. The results are shown in Table 1. In the table, relative sensitivity is expressed with the sensitivity value when Sample No. 1 was processed with color developer-(1) as 100. Note that the sensitivity and maximum color density value were measured using a PDA-65 type density measuring device manufactured by Konishiroku Photo Industry Co., Ltd.

[Table] As is clear from Table 1, samples 1 to 3 containing only the cyan coupler of the present invention cannot obtain sufficient color density even when processed with the color developer (1) containing benzyl alcohol. Furthermore, when processed with a color developing solution (2) that does not contain benzyl alcohol, the color density and sensitivity decrease. Furthermore, in samples Nos. 4 to 6 in which conventionally used phenol compounds other than the present invention were combined with the cyan coupler of the present invention,
No increase in sensitivity or color development was observed in any of the samples, and on the contrary, the results were worse than Samples 1 to 3. However, samples No. 7 to 1, which are combinations of the cyan coupler of the present invention and the phenol derivative of the present invention,
In No. 11, an increase in sensitivity and color development was observed in all cases. Furthermore, even when processed with Color Developer 1 which does not contain benzyl alcohol, the effects of the present invention were surprising. [Example 2] On a support made of subbed polyethylene-coated paper, the following layers were sequentially coated from the supporting side to produce a multicolor photographic material. 1st layer: Blue-sensitive silver halide emulsion containing yellow coupler (silver chlorobromide emulsion containing 90 mol% silver bromide, 300 g of gelatin per mole of silver halide)
(including g) was coated and dried so that the coated gelatin amount was 2 g/m ² . 2nd layer: 1st intermediate layer (coated gelatin 1.5g/m ²
3rd layer: Green-sensitive silver halide emulsion containing a magenta coupler (silver chlorobromide emulsion containing 80 mol% silver bromide, containing gelatin per mol of silver halide)
(containing 400 g) was coated and dried so that the coated gelatin amount was 2 g/m ² . 4th layer: second neutral layer containing UV absorber (gelatin layer with coated gelatin 1.5 g/ ^m2 ) 5th layer: red-sensitive silver halide emulsion containing cyan coupler (80 mol% silver bromide) Silver chlorobromide emulsion containing 300 g of gelatin per mole of silver halide
) was coated and dried so that the amount of gelatin coated was 2 g/m ² . 6th layer: Third intermediate layer containing UV absorber (gelatin layer with coated gelatin 1.5g/m ² ) 7th layer: Protective layer (gelatin layer with coated gelatin 1.5g/m ² )

[Table] In the table, the amount of couplers added in the first layer, third layer, and fifth layer is shown per 1 mole of silver halide, and the amount of phenol derivative, high boiling point solvent, and antioxidant is expressed in mol%. The amount of ^the ultraviolet absorber in the fourth layer and the sixth layer and the antifoggant in each layer is expressed in g/m ² based on the weight of the coupler. The high boiling point solvent in the 6th layer indicates the amount added per unit m ² , g/
Expressed in ^m2 . Each sample obtained with the configuration shown in Table 2 above was processed using color developer (1) according to the processing steps shown in Example 1. As a result, each sample had a stable color balance. It turned out to be a silver color photographic material. Example 3 Regarding samples No. 2 and 8 shown in Table 1 above,
Samples using dibutyl phthalate as a high-boiling solvent and samples using phosphoric acid ester-based and acid amide-based high-boiling solvents were processed using color developer (1) according to each processing step shown in Example 1. Table 3 shows the maximum color density and fog density for the results.

[Table] As is clear from Table 3, samples No. 2 and 16~
In samples other than the present invention shown in No. 19, no superiority in color density was observed between the three types of high boiling point solvents. However, in Samples 8 and 16 to 19, in which the cyan coupler of the present invention and a phenol derivative were combined, the phthalate diesters of HBS-4 and HBS-9 were used in addition to the phosphoric acid ester type and acid amide type. It is understood that the color density was higher than that of samples No. 21 to 23 using high boiling point solvents, and the superiority of phthalic acid diester as a high boiling point solvent was recognized. Example 4 For samples No. 2 and 8 shown in Table 3, the antifoggant (A-1) was adjusted to 0.01 g/m ² per unit m ² and the antifoggant (A-1) was added and not added. The samples were treated in the same manner as in Example 3, and the results are shown in Table 4.

[Table] As is clear from Table 4, although the antifoggant effect was observed in Samples No. 2 and 24, it was still insufficient. However, by combining it with the phenol derivative of the present invention, the fog density can be significantly improved, and it can be seen that the effect of using the antifoggant is remarkable.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic photosensitive material comprising a photographic cyan coupler represented by the following general formula [] and a phenol derivative represented by the following general formula [] in a photographic constituent layer. material. General formula [] [In the formula, R ₁ represents a hydrogen atom or a halogen atom,
R ₂ represents an alkyl group or an acylamino group, and R ₃
represents an aryl group, and Z represents a hydrogen atom or a group capable of being eliminated during a coupling reaction with an oxidation product of a color developing agent. ] General formula [] [In the formula, R ₄ represents an alkyl group, aryl group, alkoxy group or amino group, R ₅ represents a monovalent group, n represents an integer from 0 to 3, and n is 2
In the above cases, R ₅ may be the same or different.