JPH0521219B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material containing a photographic coupler for improving sharpness and graininess. (Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic primary amine color developing agent and a coupler react to produce indophenol, indoaniline, indamine, azomethine, etc.
It is known that phenoxazine, phenazine and similar dyes can be produced to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indasolone coupler is mainly used. phenolic couplers, such as phenols and naphthols, are used primarily to form cyan images. In recent years, with the spread of disk cameras and 110 size cameras, high image quality has become more important than ever for silver halide photographic materials, especially color photographic materials. In particular, it is important to improve sharpness and graininess. It has been known that couplers are used not only to form dye images but also to release photographically useful groups. Compounds that release photographically useful groups are used for various purposes such as improving color reproducibility, improving graininess, improving sharpness, or increasing sensitivity. Now, couplers have been proposed that can release a compound that captures an oxidized color developing agent from the coupling position of the coupler. For example, JP-A-52
-28318, No. 57-111537, and No. 57-138636 are known. These couplers are used for the purpose of improving graininess or controlling gradation, but their effects are weak and further improvements have been desired. It has also been found that the scavengers for the oxidized developing agent released by these known couplers not only have a weak scavenging ability but also have low diffusivity. Therefore, the sharpness could not be improved, and it was not possible to diffuse into other layers to obtain a multilayer effect. (Problems to be Solved by the Invention) Therefore, an object of the present invention is to reduce the graininess by incorporating a novel coupler that releases a compound that captures the oxidized developing agent upon reaction with the oxidized developing agent. An object of the present invention is to provide a color photographic material that is excellent in sharpness or color reproducibility due to a multilayer effect. (Means for Solving the Problems) The above object has been achieved by a silver halide color photographic light-sensitive material containing a coupler represented by the following general formula []. General formula [] [In the formula, A represents a coupler residue that cleaves with X upon reaction with an oxidized developing agent, X represents an oxygen atom, and R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. where R ₃ represents a substituent, n represents 0, 1 or 2, and when n is 2, the two R _3s may be different substituents;
Two of R ₁ , R ₂ and R ₃ may be divalent groups and connected to form a cyclic structure. ] In the compound of the present invention, an aromatic alcohol or an aromatic thiol to which two (or more) sulfonamide groups are bonded is released by reaction with an oxidized developing agent. One of the sulfonamide groups must be in the para position to X. It is believed that this precisely explains the superior performance of the present invention. That is, when bissulfonamide phenol or bissulfonamide thiophenol is separated from A, these compounds exhibit a strong reducing action and reduce the oxidized developing agent. Also, 2
The two sulfonamide groups moderately increase water solubility and increase diffusibility. Furthermore, the diffusivity can be easily adjusted by adjusting the size of R ₁ , R ₂ or R ₃ . A coupler in which sulfonamide groups are bonded to the 2nd and 5th positions of
Although disclosed in No. 138636, the compound separated from this coupler had a fatal defect in that the oxidized developing agent caused a coupling reaction at the para position of the hydroxyl group. Therefore, there was a problem that the reducing property was weak and the color became cloudy due to the dye produced by the coupling reaction. No such defect is observed in the compounds of the present invention. Further, US Pat. No. 4,401,752 discloses an example of a coupler that leaves off a phenoxy group having a sulfonamide group in the ortho position. This coupler is used for the purpose of improving color density, and particularly for reducing the amount of developed silver (equivalence) per amount of dye produced. It has shown some performance for this purpose, producing dyes at amounts of silver close to the theoretically required 2 equivalents of silver. However, the couplers of the present invention in which the sulfonamide group leaves off the phenoxy group which it has in the para position as well as the ortho position do not function as two-equivalent couplers. This is because the compound released from the coupler exhibits strong reducing properties and reduces the oxidized developing agent. In other words, the equivalence is increased, and a large amount of silver is required to obtain the same color density. In other words, the coupler of the present invention cannot be used as a 2-equivalent coupler for the purpose of increasing color density. When the coupler of the present invention is used, excess oxidized developer generated during development can be reduced and effectively removed. This prevents individual pigment clouds from growing beyond a certain level, prevents malt formation, and improves graininess. Furthermore, with the couplers of the present invention, edge effects and interlayer effects were observed when the reducing agent released from the couplers was highly diffusive. This effect was particularly noticeable in color reversal sensitive materials. For example, it has been known to use couplers that release development inhibitors (DIR couplers) for the purpose of edge effects and interlayer effects. However, the current situation is that conventional DIR couplers cannot be used in color reversal sensitive materials because they do not have the effect of inhibiting development. This is because conventional DIR couplers use a type of inhibitor that adsorbs to silver halide, which does not have a development inhibitory effect in color reversal processing with high development activity. However, the coupler of the present invention showed excellent graininess improvement effects and sharpness improvement effects even when used in color reversal sensitive materials. That is, the compound released from the coupler of the present invention in the second development of the color reversal process is:
It functions as a capture agent for oxidized developing agent and consumes the oxidized developing agent. As a result, developable silver is consumed and color development is suppressed, resulting in the DIR effect. The invention will be explained in detail below. In the general formula [], X is preferably an oxygen atom. In the general formula [], when R ₁ and R ₂ represent an aliphatic group, it has 1 to 32 carbon atoms, preferably 1 to 18 carbon atoms, and is substituted or unsubstituted, linear or branched, chained or cyclic, saturated or unsaturated. It can be either. Examples of substituents include those listed below: halogen atom, aryl group, alkoxy group, aryloxy group, arylthio group, alkoxycarbonyl group, hydroxyl group, acylamino group, cyano group, nitro group, carbamoyl group, sulfamoyl group. , sulfonamide group, acyloxy group, alkylthio group, amino group, sulfonyl group, acyl group, ureido group, or aryloxycarbonyl group. When these substituents contain an aliphatic group, they have 1 to 16 carbon atoms, and may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted. When the above substituent includes an aromatic group, the number of carbon atoms is 6.
-10, preferably a substituted or unsubstituted phenyl group. In the general formula [], when R ₁ and R ₂ represent an aromatic group, the number of carbon atoms is 6 to 10, and preferably a substituted or unsubstituted phenyl group. Substituents include aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, alkoxy groups, aryloxy groups, arylthio groups, alkoxycarbonyl groups, hydroxyl groups, acylamino groups, cyano groups, nitro groups, carbamoyl groups, and sulfamoyl groups. , sulfonamide group, acyloxy group, alkylthio group, amino group, sulfonyl group, ureido group, aryloxycarbonyl group, carboxyl group, acyl group, alkoxycarbonylamino group, or sulfamoylamino group. When these substituents include an aliphatic group, the number of carbon atoms is 1 to 32, preferably 1 to 16, and may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted. It may be. When the above substituent includes an aromatic group, it has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group. In addition, when the above substituent contains a heterocycle, for example, imidazole, pyrrole, thiophene, tetrahydrofuran, benzimidazole, pyridine,
triazole, pyrazole imidazolidine-2,
It has a ring structure such as 4-dione. When R ₁ and R ₂ represent a heterocyclic group in the general formula [], a 5- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom, an oxygen atom, or a selenium atom is preferred as the hetero atom. For example, imidazole, pyrazole, 1,2,4-triazole, thiophenefuran, benzimidazole, pyridine, tetrahydrofuran, etc. These may have substituents, and preferred substituents include aliphatic groups, aromatic groups, and acylamino groups. , sulfonamide group, alkoxy group, halogen atom, aryloxycarbonyl group, alkoxycarbonyl group, alkylthio group, ureido group, cyano group, aamino group, aryloxy group, etc. When these substituents include an aliphatic group, the number of carbon atoms is 1.
-32, preferably 1-16, and may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted. In addition, when the above substituent includes an aromatic group, the number of carbon atoms is 6 to
10, preferably a substituted or unsubstituted phenyl group. In the general formula [], R ₃ is preferably an aliphatic group, an aromatic group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, a thioureido group, an acylamino group, a cyano group, or a nitro group. , carbamoyl group, sulfmoyl group, sulfonamido group, acyloxy group, alkylthio group, amino group, sulfonyl group, ureido group, aryloxycarbonyl group, alkoxycarbonylamino group, sulfamoyltamino group, acyl group, or n is 2 When

[Formula] (R ₄ is synonymous with R ₃ ). When these substituents contain an aliphatic group, they have 1 to 32 carbon atoms, preferably 1 to 16 carbon atoms, and may be linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted. It may be hot. Also
When R ₃ includes an aromatic group, the number of carbon atoms is 6 to
10, preferably a substituted or unsubstituted phenyl group. In the general formula [], A is specifically a coupler residue represented by the following general formula (), (), (), (), (), () or (). In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group (in the general formula []). In the above formula, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ ,
When R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ or R ₁₇ contains a diffusion-resistant group, it has a total number of carbon atoms of 8 to 32, preferably
selected to be between 10 and 22, otherwise
The total number of carbon atoms is preferably 15 or less. Next, R ₅ to R ₁₇ and l in the general formulas () to () will be explained. In the formula, R ₅ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₆ represents an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R ₅ preferably has 1 to 22 carbon atoms, and may be substituted or unsubstituted, chain or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as _R5 are:
Such as: isopropyl, isobutyl, tert-butyl, isoamyl, tert-
amyl group, 1,1-dimethylbutyl group, 1,1-
Dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 1-methoxyisopropyl group, 1-phenoxyisopropyl group, 1-p-
tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimido)isopropyl group,
α-(benzenesulfonamido)isopropyl group, etc. R ₅ or R ₆ is an aromatic group (especially phenyl group)
In this case, the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total of 1 to 22 carbon atoms. The phenyl group represented by R ₅ or R ₆ further includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms. Alternatively, it may be substituted with a halogen atom. Furthermore, R ₅ or R ₆ may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, and the like. These substituents may themselves have further substituents. When R ₅ represents an alkoxy group, the alkyl portion has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.
represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ₅ or R ₆ represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group, respectively. combine. Such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine,
An example is oxazine. These may further have a substituent on the ring. In the general formula [], R ₇ has a carbon number of 1 to 32
Preferably 1 to 22 linear or branched alkyl groups (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g., allyl groups, etc.), cyclic alkyl groups (e.g., cyclopentyl, cyclohexyl, etc.). , norbornyl group), aralkyl group (e.g. benzyl,
β-phenylethyl group, etc.), cyclic alkenyl group (e.g. cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups, alkylthiocarbonyl groups. , arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Sulfo group, sulfamoyl group, carbamoyl group,
Acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, It may be substituted with an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group, or the like. Furthermore, R ₇ is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may have an N-arylanilino group, an N-acylanilino group, a hydroxy group, etc. More preferred as R ₇ is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. It is useful because there are few colors. Furthermore, R ₇ is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, or a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, or a benzothiazolyl group) , oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), heterocyclic group substituted with the substituent listed for the preceding aryl group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group , an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R ₈ is a hydrogen atom, a straight chain or branched alkyl having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms,
alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (which may carry the substituents listed for the preceding group R ₇ ), aryl groups and heterocyclic groups (which carry the substituents listed above for R ₇ ). ), alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.),
Aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy, ethoxy, heptadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4-di-
tert-aminophenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.) , ureido groups (e.g. ureido, N-arylureido, N
-alkylureido group), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5
-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. -pyridylamino group, 2-benzoxazolylamino group, etc.),
Alkylcarbonyl group (e.g. methylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents either a cyano group or a hydroxy group. In the formula, R ₉ represents an aliphatic group or an aromatic group. The aliphatic group preferably has 1 to 22 carbon atoms.
It may be substituted or unsubstituted, linear or cyclic. Preferred substituents include an alkoxy group, an alkylthio group, an aryloxy group, a carboxyl group, a halogen atom, and an acylamino group, which may themselves have further substituents. Specific examples of aliphatic groups useful as _R9 are: dodecyl, hexadecyl, dodecyloxypropyl, cyclohexyl, tert-butyl, butyl, 3-(2,
4-di-tert-amylphenoxy)propyl group,
1-(2,4-di-tert-amylphenoxy)propyl group, etc. When R ₉ represents an aromatic group, it may have the substituents listed above when R ₅ is an aryl group. In the formula, _R10 is an aliphatic group (e.g. methyl group, ethyl group, etc.), a halogen atom (e.g. chlorine atom,
atom), alkoxy groups (e.g. methoxy group,
ethoxy group) or an aromatic group (eg, phenyl group). In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom, an aliphatic group, or an aromatic group. _R11 or
When R ₁₂ represents an aliphatic group, it has 1 to 32 carbon atoms, preferably 1 to 18 carbon atoms, and may be substituted or unsubstituted, linear or cyclic. Preferred substituents include an aryloxy group, an alkoxy group, a halogen atom, an aryl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group,
These may further have a substituent such as an acyloxy group. Specific examples of useful aliphatic groups for R ₁₁ or R ₁₂ are: dodecyl, hexadecyl, dodecyloxypropyl, cyclohexyl, tert-butyl, 3-
(2,4-di-tert-amylphenoxy)propyl group, 1(2,4-di-tert-amylphenoxy)
propyl group, etc. When R ₁₁ or R ₁₂ represents an aromatic group, it has 6 to 10 carbon atoms, preferably a substituted or unsubstituted phenyl group. Preferred substituents include alkoxy groups, aliphatic groups, acylamino groups, alkoxycarbonyl groups, halogen atoms,
These include a sulfonamide group, a sulfamoyl group, a carbamoyl group, a carboxyl group, a hydroxyl group, a cyano group, a nitro group, and the like. Specific examples of useful aromatic groups for R ₁₁ or R ₁₂ are: 2-tetradecyloxyphenyl, 4-
They include a tetradecyloxyphenyl group, a 3-dodecyloxycarbonylphenyl group, a 2-chloro-5-dodecyloxycarbonylphenyl group, a phenyl group, a 4-carboxyphenyl group, and the like. In the formula, R ₁₃ is a halogen atom, an acylamino group (e.g., acetamido group, 2,4-di-tert-
amylphenoxyacetamide group), sulfonamide group (e.g. methanesulfonamide group, hexadecylsulfonamide group), alkoxy group (e.g. methoxy group, dodecyloxy group), or aliphatic group (e.g. methyl group, ethyl group). represent In the formula, l represents 0, 1 or 2, and when l is 2, the two substituents may be the same or different. _R14 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and preferably 1 to 22 carbon atoms. represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, such as an alkoxy group,
Alkoxycarbonyl group, acylamino group, alkylsulfamoyl group, alkylsulfonamide group, alkylsuccinimide group, halogen atom,
Examples include nitro group, carboxyl group, nitrile group, alkyl group, and aryl group. _R15 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, and preferably 1 to 22 carbon atoms. alkoxycarbonyl group or aryloxycarbonyl group, alkanesulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, arylsulfonyl group, aryl group, 5- or 6-membered heterocyclic group (heteroatoms include nitrogen atom, oxygen atom,
represents a sulfur atom (for example, a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group), which has a substituent as described above for _R14 . Good too. In the general formula [], R ₁₆ represents an aliphatic group, an aromatic group, a heterocyclic group or an anilino group. Regarding the aliphatic group, aromatic group or heterocyclic group, the explanation for R ₅ applies. When R ₁₆ represents an anilino group, the substituent for the phenyl group is
When R ₇ is a phenyl group, it may have the listed substituents. Preferred examples of R ₁₆ include pentafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, p-cyanoanilino group,
Examples include 3,4-dichloroanilino group, p-propanesulfonylanilino group, and 2-ethanesulfonamidophenyl group. In the formula, R ₁₇ represents an aliphatic group or an aromatic group. The explanation for _R5 applies to these. Preferred examples of R ₁₇ include tert-butyl group,
1-(2,4-di-tert-amylphenoxy)propyl group, 1-(2,4-di-tert-amylphenoxy)pentyl group, isoamyl group, 1-(2,
Examples include 4-di-tert-octylphenoxy)heptyl group. The coupler of the present invention is preferably used in a silver halide emulsion layer or a layer adjacent thereto, and is preferably used in combination with a conventional photographic color coupler. The amount of the coupler of the present invention used (the ratio of the coupler of the present invention/normal photographic color coupler) is 5/95 to 110/
0 is preferable, and 10/90 to 60/40 is more preferable. Examples of the compounds used in the present invention include, but are not limited to, the following compounds. Synthesis of Exemplary Compound (1) Synthesis was performed using the following synthetic route. Synthesis of compounds 3 ~ 1,4-dihydroxy-2-naphthoic acid 204
386 g of a methanol solution (28%) of sodium methoxide was added to a solution of 500 ml of dimethylformamide. After stirring for 10 minutes,
To this reaction solution, 300 ml of a solution of 186 g of 2,4-dinitrofluorobenzene in dimethylformamide was added dropwise at room temperature. After continuing stirring for 2 hours, 101.4 g of concentrated hydrochloric acid was gradually added to the reaction solution. The precipitated crystals were collected, washed with water, and dried to obtain 3 to 274 g of the compound. Synthesis of Compound 4 ~ Compound 3 ~ Add 40 ml of a chloroform solution of 160.4 g of dicyclohexylcarbodiimide (DCC) to a mixture of 274 g, o-tetradecyloxyaniline, 226 g, and 2.5 g of dimethylformamide at 10°C.
was dripped. After stirring for 4 hours, the reaction solution was filtered, and 200 ml of water was slowly added dropwise to the solution. By collecting the precipitated crystals and drying them, 292 g of Compounds 4 to 4 were obtained. Synthesis of exemplified compound (1) 500 g of reduced iron, 30 g of ammonium chloride, acetic acid
A mixture of 30 ml water, 350 ml isopropyl alcohol and 2.5 ml was reduced for 10 minutes. In this reaction solution,
Under reflux, 292 g of compounds 4 to 4 were gradually added. 30
After a few minutes, the reaction solution was filtered and the solution was concentrated.
78.5 g of benzenesulfonyl chloride dissolved in 1 part of tetrahydrofuran
was added dropwise at room temperature. In addition, 35.1g of pyridine
was added dropwise, and the mixture was stirred for 12 hours. The reaction solution was extracted with ethyl acetate, and the organic layer was washed with water. After further drying with sodium sulfate, the solvent was distilled off, and the obtained concentrate was recrystallized with a mixed solution of acetonitrile and ethyl acetate.
273.2 g of Exemplified Compound (1) was obtained. (mp167.0°C) Synthesis of Exemplified Compound (2) The same method as Synthesis Example (1) was used except that methanesulfonyl chloride was used instead of benzenesulfonyl chloride in the step of Synthesis Example (1). Synthesized. (mp 146.0°C) The coupler of the present invention is preferably used in combination with a commonly used photographic coupler. The desired effect of the present invention can be obtained by using it in an amount of 10 ^-2 to 1.0 mol, preferably 0.1 to 0.8 mol, per mol of the dye-forming coupler used in the same layer. The coupler of the present invention or the couplers that can be used in combination as described below can be introduced into the photosensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. This can be cited as a typical example. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of 175°C or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents are described in US Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, limit filtration, or the like before use for coating. Specific examples of high-boiling organic solvents include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecylphthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, trichloromethane, etc.), Dyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc. ), benzoic acid esters (2-
ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols, (isostearyl alcohol, 2,4-di-tert- amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-
(2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and as co-solvents, those with a boiling point of about 30°C to about 160°C can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. The process and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat. No. 4,199,363;
It is described in OLS No. 2541274 and OLS No. 2541230, etc. A variety of color couplers can be used in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye by reacting with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in Research Disclosure (RD) 17643 (1978).
18717 (November 1979). The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is preferred to a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used. A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention;
U.S. Patent No. 3408194, U.S. Patent No. 3447928, U.S. Patent No.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density. Examples of magenta couplers that can be used in the present invention include oil-protected indazolone or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrozolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Representative examples thereof include U.S. Pat.
No. 2600788, No. 2908573, No.
It is described in No. 3062653, No. 3152896, No. 3936015, etc. A two-equivalent 5-pyrozolone coupler is preferred because it can provide high color density and high sensitivity with a small amount of coated silver, and as a leaving group, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the nitrogen atom leaving group described in US Pat. No. 4,351,897 is preferred. Particularly preferred are arylthio groups. Furthermore, the ballast group described in European Patent No. 73636 also has the effect of increasing color density for 5-pyrozolone couplers. As a pyrazoloazole coupler, U.S. Patent No.
Pyrazolobenzimidazoles described in No. 3369897,
Preferably, the pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. ) are mentioned. Imidazo[1,
2-b] Preferred are pyrazoles, as described in European Patent No.
Pyrazolo [1,5-b] [1,
2,4] triazoles are particularly preferred. Cyan couplers that can be used in the present invention include:
There are oil-protected naphthol-based and phenolic couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293, U.S. Pat. No. 4,052,212, U.S. Pat.
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in No. 1 and No. 4,296,200. Further, specific examples of phenolic couplers are described in US Pat. Nos. 2,369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, typical examples being the phenolic cyan couplers described in U.S. Pat. No. 3,772,002, U.S. Pat. No. 2,772,162;
Same No. 3758308, Same No. 4126396, Same No. 4334011,
2,5-diacylamino-substituted phenolic couplers described in U.S. Pat.
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in Nos. 4451559 and 4427767. The coupler of the present invention and the above-mentioned couplers can be used in combination in the same layer in order to satisfy the characteristics required for a photosensitive material, or the same compound can be added in two or more different layers. Of course it doesn't matter. The dye-forming coupler is used in an amount of 0.002 to 0.5 mole per mole of light-sensitive silver halide in the layer to which it is added. In color photosensitive materials for photography, yellow coupler is
0.01 to 0.5 mole of magenta coupler, 0.003 to 0.25 mole of magenta coupler, and 0.002 to 0.12 mole of cyan coupler are often used, and in color photosensitive materials for printing such as color paper, yellow, magenta, and cyan couplers are all photosensitive silver halide. Although 0.1 to 0.5 mol per mol is often used, it is possible to design photosensitive materials outside this range. In order to correct unnecessary absorption in the short wavelength range of the magenta and cyan coupler chromophores, it is preferable to use colored couplers in combination with the Salar photosensitive material for photographing. Yellow-colored magenta couplers described in U.S. Pat.
Typical examples include magenta-colored cyan couplers described in No. 4138258 and British Patent No. 1146368. These color couplers may form a dimer or more polymer. Typical examples of polymerized couplers are described in US Pat. No. 3,451,820 and US Pat. No. 4,080,211. Specific examples of polymerized magenta couplers are given in UK Patent No. 2102173 and US Patent No.
Described in No. 4367282. In addition, chromophoric diffusive couplers can be used in combination to improve graininess; examples of such couplers are described in US Patent No. 4366237 and British Patent No. 2125570, and European Patent No.
Specific examples of yellow, magenta and cyan are described in No. 1 and OLS 3324533. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used alone or in conjunction with gelatin. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as spherical shapes, or these crystals may have irregular crystal shapes such as spherical shapes. It can also be a composite of shapes. In addition, research day closure
22534, in which tabular grains having a thickness of 0.5 microns or less, a diameter of at least 0.6 microns, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area. The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides of different compositions may be joined by epitaxial bonding. , may consist of a mixture of particles of various crystalline forms. Further, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle. The grain size of the silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967) Written by G.F. Duffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, there is a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Silber−halogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, beramobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azaindenes, e.g. triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the basic heterocyclic nuclei commonly used for cyanine dyes can be used. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. The present invention
It is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected according to need. A cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer,
Usually, each blue-sensitive emulsion layer contains a yellow-forming capter, but different combinations may be used depending on the case. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, active vinyl compounds (1,3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Pat.
Aryl group-substituted benzotriazoles described in US Pat. No. 3533794, US Pat. Patent No. 3705805 and the same
cinnamic acid esters as described in US Pat. No. 3,215,530 and British Patent No. 1,321,355; Molecular compounds can be used. Ultraviolet absorbing fluorescent brighteners described in US Pat. Nos. 3,499,762 and 3,700,455 may also be used. A typical example of a UV absorber is RD24239 (1984
(June 2015), etc. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, osasonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful flexible supports include:
These include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, and polycarbonate, and papers coated or laminated with baryta layers or α-olefin polymers (e.g., polyethylene, polypropylene), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. Examples of white pigments include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate, but titanium dioxide, barium sulfate, and zinc oxide are Particularly useful. The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. When using these supports for reflective materials,
In addition to the support and emulsion layer, a hydrophilic colloid layer containing a white pigment at a high density can be provided to improve the whiteness and the sharpness of the photographic image. In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, and sharpness can be achieved. In addition to improving the optical clarity, a photographic image with particularly excellent saturation and depiction of dark areas can be obtained, which is particularly preferable. In this case, polyethylene terephthalate and cellulose acetate are particularly useful as raw materials for the synthetic resin film, and barium acetate and titanium oxide are particularly useful as white pigments. In addition to the above, various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc., may be added to the color photographic material of the present invention as necessary. An example can be found in Research Disclosure 17643. Furthermore, in some cases, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, or silver bromide emulsion)
may be added. Color developing solutions that can be used in the present invention include:
Preferred is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, 4
Typical examples include -amino-3-methyl-N-ethyl-N-β-methoxyethylaniline. The color developing solution contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, and as described in OLS 2,622,950. It may also contain antioxidants and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, Complex salts of organic acids such as tartaric acid and malic acid: persulfates, manganates;
Nitrosphenols and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. It may be washed with water after color development or bleach-fixing treatment. Color development can be carried out at any temperature between 18°C and 55°C. Color development is preferably carried out at 30°C or higher, particularly preferably at 35°C or higher. The development time is preferably as short as about 3 and a half minutes to about 1 minute. For continuous development processing, liquid replenishment is preferred, and 330 c.c. to 160 c.c., preferably 100 c.c. or less, of the liquid is replenished per square meter of processing area. The amount of benzyl alcohol in the developer is preferably 20 ml or less, preferably 10 ml or less. Bleach-fixing can be carried out at any temperature between 18°C and 50°C.
The temperature is preferably 30°C or higher. When the temperature is 35°C or higher, the processing time can be reduced to 1 minute or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and washing can be done within 1 minute using a stabilizing bath. Colored pigments deteriorate and fade not only due to light, heat, and temperature, but also due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold preventive agent. Specific examples of antifungal agents include 2 as described in JP-A-57-157244.
-There are thiazolylbenzimidazoles. The antifungal agent may be incorporated into the photosensitive material, or may be added from the outside during the development process, or may be added at any process if it coexists with the photosensitive material in the processing agent. The present invention can be used for general silver halide color photosensitive materials such as color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies, and color reversal film for TV. In particular, when used in color negative films, especially color reversal films, which require high sensitivity and high image quality, remarkable effects can be obtained in improving sharpness and graininess. The present invention can be applied to light-sensitive materials that use a black coupler system or a three-color coupler mixing system. For a detailed explanation of the black coupler method, see U.S. Pat. No. 3,622,629, U.S. Pat.
No. 105248, and the three-color coupler mixing method is described in detail in Research Disclosure 1712, etc. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 Sample [1] was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with an undercoating layer. 1st layer Low-sensitivity red-sensitivity emulsion layer 100g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-amylphenoxy)butyramide}phenol (coupler) cresyl phosphate 100c.c.
500 g of emulsion obtained by dissolving in 100 c.c. of ethyl acetate and stirring at high speed with 1 kg of 10% gelatin aqueous solution and 10 g of surfactant sodium dodecylbenzenesulfonate.
g is red-sensitive low-sensitivity silver iodobromide emulsion 1 kg (average grain size of silver halide grains 0.3μ, silver 70 g, gelatin
60g (containing iodine content 3 mol%) and gelatin,
Water, stabilizers, coating aids, etc. were added and mixed, and coated to a film thickness of 2 μm after drying. (Amount of silver 0.6
g/m ² ) 2nd layer Medium-sensitivity red-sensitivity emulsion layer 1 kg of cyan coupler emulsion used in the 1st layer
1 kg of red-sensitive, medium-sensitive silver iodobromide emulsion (average grain size of silver halide grains 0.5μ, 70 g of silver, gelatin)
60g (contains iodine content 3 mol%), gelatin, water,
Add stabilizers, coating aids, etc., mix, and adjust the dry film thickness.
It was applied to a thickness of 1μ. (Amount of silver 0.4 g/m ² ) Third layer Highly sensitive red-sensitive emulsion layer 1 kg of the emulsion of the coupler used in the first layer was mixed with 1 kg of red-sensitive and highly sensitive silver iodobromide emulsion (average grain size of silver halide grains 0.6 70 g of μ silver (containing 60 g of gelatin, iodine content: 3 mol %) was mixed with gelatin, water, a stabilizer, a coating aid, etc., and coated to a dry film thickness of 1 μ. (Amount of silver 0.4 g/m ² ) 4th layer Intermediate layer 2,5-di-sec-octylhydroquinone 200
Dissolve g in 200 c.c. of ethyl acetate, add 1 kg of 10% aqueous gelatin solution and sodium dodecylbenzenesulfonate.
An emulsion obtained by stirring 20 g at high speed was mixed with gelatin, water, a coating aid, etc., and coated to a dry film thickness of 1 μm. 5th layer Low green sensitivity emulsion layer Magenta coupler 1-{2,4,6-trichlorophenyl)-3-{3-(2,4 di-t-amylphenoxyacetamide)benzamide}-5-
500 g of the emulsion obtained in the same manner as the emulsion of the first layer except that pyrazolone was used was mixed into 1 kg of green-sensitive low-sensitivity silver bromide emulsion (average grain size 0.3μ, containing 70 g silver, 60 g gelatin, iodine content 3). mol%) and gelatin,
Water, a stabilizer, and a coating aid were mixed and coated to a dry film thickness of 2μ. (Amount of silver: 0.7 g/m ² ) 6th layer Medium-sensitivity green-sensitivity emulsion layer 1 kg of magenta coupler emulsion used in the 5th layer
Green-sensitive, medium-sensitive silver iodobromide emulsion 1Kg (average grain size 0.5μ, containing 70g silver, 60g gelatin, iodine content 3)
(mol%), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness of 1μ. (Amount of coated silver: 0.4 g/m ² ) 7th layer Highly sensitive green-sensitive emulsion layer 1 kg of magenta coupler emulsion used in the 5th layer
, mixed with 1 kg of green-sensitive, highly iodine-sensitive silver bromide emulsion (containing 70 g of silver with an average grain size of 0.7 μm and 60 g of gelatin, iodine content of 3 mol %), gelatin, water, stabilizers, coating aids, etc. The film was coated to a dry film thickness of 1 μm. (Coated silver amount 0.4g/m ² ) 8th layer Intermediate layer 1 kg of the emulsion used in the 4th layer was mixed with gelatin, water,
It was mixed with a coating aid and coated to a dry film thickness of 0.5μ. 9th layer Yellow filter layer Yellow colloidal silver and gelatin mixed, dry film thickness
It was applied to a thickness of 1μ. 10th layer Low-sensitivity blue-sensitivity emulsion layer Yellow coupler, α-(pivaloyl)-α-
(1-Benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used instead of the cyan coupler in the first layer, and tricresyl phosphate was added at 120
cc, 1 kg of emulsion prepared by changing ethyl acetate to 120 c.c. was converted into 1 kg of blue-sensitive low-iodophilic silver bromide emulsion (average grain size 0.5 μ, containing 70 g silver, 60 g gelatin, iodine content 3 mol%). ) was mixed with gelatin, water, a stabilizer, and a coating aid, and coated to a dry film thickness of 2μ. (Amount of coated silver: 0.6 g/m ² ) 11th layer: Intermediate blue-sensitive emulsion layer 1 kg of emulsion of the yellow coupler used in the 10th layer
1 kg of blue-sensitive medium-sensitive silver iodobromide emulsion (average grain size
0.6μ, silver 70g, gelatin 60g, iodine content 3 mol%), gelatin, water, stabilizers, coating aids, etc. were mixed and coated to a dry film thickness of 1μ. (Amount of silver coated
0.4g/m ² ) 12th layer Highly sensitive blue-sensitive emulsion layer 1Kg of yellow coupler emulsion used in layer 10
, mixed with 1 kg of blue-sensitive silver iodobromide emulsion (average grain size 0.7μ, containing 70 g silver, 60 g gelatin, iodine content 3 mol%), gelatin, water, stabilizer, coating aid, etc. Then, it was applied to a dry film thickness of 1 μm. (Coated silver amount 0.4g/ ^m2 ) 14th layer 2nd protective layer UV absorber, 5-chloro-
2-(2-hydroxy-3,5-di-t-butylphenyl)-2H-benzotriazole 15g, 2-
(2-hydroxy-5-t-butylphenyl)-
30 g of 2H-benzotriazole, 35 g of 2-(2-hydroxy-3-sec-butyl-5-t-butylphenyl)-2H-benzotriazole, dodecyl-
100 g of 5-(N,N-diethylamino)-2-benzenesulfonyl-2,4-pentadienoate, 200 c.c. of tricresyl phosphate, 200 c.c. of ethyl acetate
Dissolved in cc, sodium dodecylbenzenesulfonate 20
1 kg of an emulsion obtained by stirring 2 kg of 10% gelatin at high speed was mixed with gelatin, water, a coating aid, etc., and coated to a dry film thickness of 2 μm. (Total UV absorber coating amount 0.5g/ ^m2 ) 15th layer 1st protective layer Fine-grain silver iodobromide emulsion that is not chemically sensitized (grain size 0.1μ, contains 70g silver and 60g gelatin, iodine content 1) (mol%) was mixed with gelatin, water, stabilizers, coating aids, etc., and coated to a dry film thickness of 1μ. (Amount of silver: 0.3 g/m ² ) The obtained multilayer coated film was designated as sample No. 1. 1/2 of the cyan coupler used in the 1st to 3rd layers
An emulsion was prepared by changing the amount of the compound of the present invention (equal mole number). Using this emulsion, samples Nos. 2 to 12 were prepared according to the method for preparing sample 1.

【table】 Samples No. 1 to No. 12 were exposed to light through a grain measurement pattern, and after color reversal processing, the RMS granularity was measured by measuring the density of the samples using a microdensity meter.
The granularity is shown at image densities of 1.0 and 2.0. Samples No. to No. 12 were exposed to light through a pattern for MTF measurement, and after color reversal processing, the samples were measured using a microdensity measuring device, and the MTF values were determined by calculation. Sharpness is expressed as an MTF value of 10 lines/mm and 20 lines/mm.

[Table] Compared to the comparative compound, the graininess and sharpness of Samples Nos. 2 to 8 using the compounds of the present invention were greatly improved. Processing process Process Time Temperature First development 6' 38℃ (±0.3) Washing 2' Reversing 2' Color development 6' Adjusting 2' Bleaching 6' Fixing 4' Washing 4' Stable 1' Dry at room temperature First development Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water and invert 1000ml Water 700ml Nitrilo. NNN-trimethylenephosphonic acid/6Na salt 3g Stannous chloride (dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water 1000ml Color development Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl -4-aminoaniline sulfate 11g Ethylenediamine 3g Add water and adjust to 1000ml Water 700ml Sodium sulfite
12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml Bleach Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron() ammonium ethylenediaminetetraacetate (dihydrate) 120.0g Potassium bromide 100.0g Add water to stabilize at 1.0 Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water to stabilize at 1.0 Water 800ml Formalin (37% by weight) 5.0ml Surfactant solution (Product name: Drywell) Add 5.0 ml of water to 1.0 Example 2 A multilayer color photosensitive material (101) consisting of each layer having the composition shown below was prepared on a transparent triacetyl cellulose film support. 1st layer; Anti-halation layer Gelatin layer containing black colloidal silver...0.15g/ ^m2 Ultraviolet absorber U-1...0.08g/ ^m2 U-2 ^... 0.12g/m22nd layer; Intermediate Layer 3rd gelatin layer containing 2,5-di-t-pentadecylhydroquinone...0.18 g/m ² Coupler C-1...0.11 g/m ² ; 1st red-sensitive emulsion layer Silver iodobromide (iodine) (Average particle size: 0.4μ)...1.2g/ ^m2 Sensitizing dye...1.4 x 10 ^-4 mol per 1 mol of silver Same...0.4 x 10 ^-4 mol per 1 mol of silver Coupler C-2...0.050g/m ² Coupler C-5...0.070g/m ² Fifth gelatin layer containing coupler C ^- 3...0.035g/m2; Intermediate layer 2,5-di-t - Gelatin layer 6th layer containing pentadecylhydroquinone...0.08g/ ^m2 ; first green-sensitive emulsion layer silver iodobromide silver iodide 4 mol% average grain size 0.4μ...0.80g/ ^m2 sensitizing dye ...4.0 x 10 ^-4 mol per 1 mol of silver Same... 3.0 x 10 ^-5 mol per 1 mol of silver Same... 1.0 x 10 ^-4 mol per 1 mol of silver Coupler C-6...0.45 g/ m ² coupler C-7...0.13 g/m ² sensitizing dye...5.6 x 10 ^-4 mol per mol of silver Same...4.0 x 10 ^-4 mol per mol of silver Coupler C-2...0.45 g/m ² coupler C-3...0.035 g/m ² gelatin layer 4th layer containing coupler C-4...0.025 g/m ² ; second red-sensitive emulsion layer silver iodobromide emulsion silver iodide 8 mol % Average particle size 0.8μ...1.0g/m ² Sensitizing dye...5.2 x 10 ^-5 mol per mol of silver Sensitizing dye...1.5 x 10 ^-5 mol per mol of silver Same...1 mol of silver Coupler C-8... ^{0.02 g} /m2 ^Coupler C-4...0.04 g/ ^m2 7th layer; 2nd green-sensitive emulsion layer Silver iodobromide Silver iodide 8 mol% Average grain size 0.8 μ...0.85 g/m ² Sensitizing dye...2.7 x 10 ^-4 mol per 1 mol of silver Same...Silver Gelatin containing 1.8 x 10 ^-5 mol per 1 mol Coupler C-6... 0.095 g/ ^{m 2} Coupler C-7... 0.015 g/m ² Layer 8: Yellow filter layer Gelatin layer containing yellow colloidal silver...0.08 g/m ² 2,5-di-t-pentadecylhydroquinone...0.090 g/m ² Ninth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodide 5 mol% Average grain size 0.3 μ...0.37 g/m ² Sensitizing dye...4.4 x 10 ^-4 mol per 1 mol of silver Coupler C-9...0.71 g/m ² Coupler C-4...0.07g/ ^m2 10th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodide 7 mol% Average grain size 0.9μ...0.55g/ ^m2 Sensitizing dye...Silver 1 3.0×10 ^-4 mol to mole Coupler C-9... 11th layer of gelatin layer containing 0.23 g/m ² ; 1st protective layer Ultraviolet absorber U-1... 0.14 g/m ² Same U-2 ...12th gelatin layer containing 0.22 g/m ² ; second protective layer silver iodobromide emulsion silver iodide 2 mol% average grain size 0.07 μ ...0.25 g/m ² polymethacrylate particles (diameter 1.5 μ) ……0.10
gelatin layer containing g/m ² In addition to the above composition, each layer contains a gelatin hardening agent H-
1 and a surfactant were applied. (Samples 102, 103) 50 mol% of coupler C-2 in the third layer of sample 101
Sample 102 and
Created 103. These samples were exposed to light for sensitometry through a red filter and subjected to color development processing as described below. Further, conventional exposure for RMS measurement was carried out, and similar color development was carried out. Photographic properties and graininess of the obtained sample were measured using a red filter. An aperture of 48μ was used for grain size measurement. The development process used here was carried out at 38°C as described below. 1 Color development...3 minutes 15 seconds 2 Bleaching...6 minutes 30 seconds 3 Washing...3 minutes 15 seconds 4 Fixing...6 minutes 30 seconds 5 Washing...3 minutes 15 seconds 6 Stability... 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0cc Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0cc Add water 1

[Table] From Table 1, it can be seen that Samples 102 and 103 of the present invention clearly have excellent graininess. Structure of compounds used in examples H-1 _CH2 =CH- _SO2 - _CH2 -CONH( _CH2 ) _2NHCO -CH2 _{- SO2} -CH
＝ _CH2

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material containing a coupler represented by the following general formula. general formula [In the formula, A represents a coupler residue that cleaves with X upon reaction with an oxidized developing agent, X represents an oxygen atom, and R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. where R ₃ represents a substituent, n represents 0, 1 or 2, and when n is 2, two R ₃ may be different substituents, and among R ₁ , R ₂ and R ₃ The two may be connected as a divalent group to form a cyclic structure. However, A does not represent the following phenol residue. Here, R _A represents a ureido group or an acylamino group, and R _B represents an acylamino group.