JPS62151847A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material superior in sharpness and capable of forming a cyan dye image high enough in density even in the case of processing it with a bleaching solution weak in oxidation power or fatigued by incorporating at least each one of specified couplers and cyan couplers in said photosensitive material. CONSTITUTION:The silver halide color photographic sensitive material contains at least one of the couplers represented by formula I and at least one of the cyan couplers represented by formulae II and III. In these formulae, A is a group to be allowed to release PDI by the coupling reaction with the oxidation product of a color developing agent; PDI is a group to be allowed to release a development inhibitor after the release of PDI by the coupling reaction with said oxidation product; R1 is an aromatic group or a heterocyclic group; R2 is a group substitutable at the naphthol ring; R3 is an aliphatic group; (a) is an integer of 0-4; (b) is an integer of 0-3; X1 is H or a group releasable by the coupling; Z2 is -O-, -S-, or R4-N=; R4 is H or an organic substituent; and Z1 is not converted into a development inhibitor or a group containing it.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a silver halide photographic material that has excellent sharpness and color reproducibility, and also provides stable high cyan color image density even when subjected to bleaching treatment using a tired bleaching solution. It is something. (Prior art) When a silver halide photographic material is exposed to light and then subjected to color development, a color developing agent such as an oxidized aromatic 7th class amine reacts with a dye-forming coupler to form a color image. . Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors of K, are formed. In this case, phenols or naphthols are often used as cyan dye-forming couplers. Many studies have been carried out on color photographic materials with the aim of improving sharpness and increasing sensitivity. A coupler that releases a development inhibitor (DIR coupler) is known as one technique for improving sharpness. For example, US Patent No. g, 2'lr. ri 6th, same da, +109.3.2j, rotation, 4t/,? <No. 0, rotation, 4t3/, /93 and same Q
, 4t77.343 and the like. However, it is still insufficient and further improvements have been desired. On the other hand, one drawback of the conventional Cyan Cub 2- is that it is difficult to obtain a cyan image of sufficiently high density in a bleaching process with weak oxidizing power. For example, if contaminated and processed through a nine-Fe(III)-EDTA bleaching step or a persulfate bleaching step, the cyan image will not be of sufficient density. This problem always exists as an unavoidable problem in the research of photosensitive materials aimed at increasing sensitivity, and improvements have long been desired. Although the above-mentioned two problems have been improved to some extent individually, there is no known means to solve them simultaneously when they are assembled as a photosensitive material. That is, it is an undeniable fact that highly sensitive photosensitive materials have poor sharpness, and photosensitive materials with excellent sharpness have low sensitivity. (Object of the Invention) The object of the present invention is to produce a silver halide color photosensitive image that has excellent sharpness and can produce a cyan image with sufficiently high density even when processed with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted. The goal is to provide materials. (Structure of the Invention) The above object is to combine at least one coupler represented by the following general formula (I) and the following general formula (n) and (III).
This was achieved by a silver halide color photographic light-sensitive material containing at least one cyan coupler represented by: General formula (I) In the formula, A represents a group that reacts with an oxidized developing agent to cleave PDl, and PDI represents a group that reacts with an oxidized developing agent to produce a development inhibitor after being cleaved from A. represent. General formula (II) General formula (III) H In the formula, R1 represents an aromatic group or a heterocyclic group, R2 represents a group that can be substituted on a naphthol ring, R3 represents an aliphatic group, and a is 0 to b represents an integer from O to 3, zl represents a hydrogen atom or a coupling-off group, and general formula (I1) and general formula (II
zl in I) represents each other or an organic substituent,
When a and b are plural, R2 in general formula (II) and general formula (I) may be the same or different, and may be bonded to each other to form a ring. In addition, in general formula (II), R2 and 12, or zl and 2
2 may be bonded to each other to form a ring. Further, a multimer of λ-mer or higher may be formed by R1% R2, R3, R4, Zl or Z2. Further, zl is not a development inhibitor or a group containing it. The compound of general formula (I) constituting the present invention is preferably one represented by the following general formula (■). General formula NV) A-(Ll)-B-(Lz)-DIv
W In the formula, A reacts with the oxidized developing agent to form (Ll) −
B (Ll) represents a group that cleaves IM, and v
WLl represents a group that cleaves B-(Ll)-DI after cleavage from A, and B cleaves B-(Ll)-DI after cleavage from A-(Ll)v and reacts with the oxidized developing agent to cleave (Ll)-DI. Ll represents a group that cleaves DI after being cleaved from B, and DI represents a development inhibitor. V and W represent θ or /. The reaction process in which the compound represented by the general formula (fl/) releases DI during development is represented by the following reaction formula. In the formula, A, Ll, B, Ll, DI, v and W represent the same meanings as explained in the general formula (IV), and T represents an oxidized developing agent. In the above reaction formula, from B-(Ll)-DI (
The reaction producing Ll)-DI characterizes the superior effectiveness of the present invention. In other words, this reaction involves T and B-(Ll)-
This is a secondary reaction with DI. The reaction rate of tsumasao depends on the concentration of each. However, where T occurs in large quantities, B-(Ll)-DI becomes (Ll)-
Generate DI immediately. W W In contrast, in places where only a small amount of T is generated, B-(Ll)-DI produces (Ll)-DI slowly W
W Yes. This reaction process combined with the above reaction process results in D
Effectively expresses the effects of I. Next, the compound represented by general formula (IV) will be explained in detail. In general formula (fV), A specifically represents a coupler residue or a redox group. When A represents a coupler residue, known ones can be used. For example, yellow coupler residues (e.g. open-chain ketomethylene type coupler residues), magenta coupler residues (e.g.!
- pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc. coupler residues), cyan coupler residues (e.g. phenol type, naphthol type, etc. coupler residues), and colorless coupler residues (e.g. indanone type, coupler residues such as acetophenone type). When A represents a redox group, in detail, the following general formula (V
). General formula (V) AI -P -(X=Y) -Q-A2 In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and at least 7 of n X and Y
represents a methine group having -(L1?B+L2), -DI as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents an integer from / to 3. (n X's and n Y's are the same or different), A1 and A2 each represent a hydrogen atom or a group that can be removed by an alkali. Here, the case where any one of λ substituents of P, X, Y% Q% A1 and A2 becomes a monovalent group and connects to form a cyclic structure is also included. For example, when (X=Y)n forms a benzene ring, a pyridine ring, etc. The groups represented by Ll and Ll in general formula (fV) may or may not be used in the present invention. It is selected as appropriate depending on the purpose. Preferably, the groups represented by Ll and Ll include the following known linking groups. (I) A group that utilizes hemiacetal cleavage reaction. For example, U.S. Patent No. 9-
/θ≦223, 39-10t224 and j
9-7j<<A group described in No. 74 and represented by the following general formula. Here, the arrow represents the bonding position on the left side in general formula (IV), and the -+-N- mark represents the bonding position on the right side in general formula (IV). represents a substituent), R5 and R6 represent a hydrogen atom or a substituent, t represents 1 or 2, t
When is 2, each of the two R5 and R6 may be the same or different, and a case where any one of R5, R6 and R7 are connected to form a cyclic structure is also included. (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. For example, timing groups as described in US Pat. (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system. For example, U.S. Patent No. g, g09.323
A group described in the above item or a group represented by the following general formula (
The group described in British Patent No. =, θ9j, 7♂3A). In the formula, the arrow represents the bonding position on the left side in general formula (IV), the cloudy yellow mark represents the bonding position on the right side in general formula (IV), and R8 and R9 represent a hydrogen atom or a substituent. In general formula (IV), the group represented by B is specifically A
-(Lz) A group or A that becomes a coupler after being cleaved from v
-(Ll) A group that becomes a redox group after being cleaved from v. For example, in the case of a phenol type coupler, the group serving as a coupler is a group that is bonded to A-(Ls)v at an oxygen atom other than a hydrogen atom of a hydroxyl group. Also! −
In the case of pyrazolone type couplers! -Hydroxypyrazole is a tautomerized type of hydroxyl group that is bonded to A-(Ll)v at the oxygen atom, which is obtained by removing the hydrogen atom. In these examples, it becomes a phenol type coupler or a j-pyrazolone type coupler only after separation from A-(Ll)V, respectively. They have (Ll)-DI at their coupling positions. When B represents a group that becomes a redox group, preferably the general formula % formula % general formula (B-/) so-P-(X'2Y') -Q-A2 where the arrow indicates A
~(Ll) represents the bonding position with v, A2, P, Q and n represent the same meanings as explained in general formula (V), and at least seven of n Y' and Y' are (Ll)
l) Represents a methine group having -DI as a substituent, and the other Y' and Y' represent a substituted or unsubstituted methine group or a nitrogen atom. Here, the case where any two substituents of A2, PXQXX' and Y' become divalent groups to form a cyclic structure is also included. In general formula (IV), DI is detailed! - aromatic substituted tetrazolylthio group,! - Aliphatic substituted tetrazolylthio group, benzimidazolylthio group, benzothiazolylthio group, benzoxazolylthio group, benzotriazolyl group, penzoindazolyl group, etc., which may have an appropriate substituent. good. In general formula (IV), A, Ll, B, Ll and D
The present application also covers cases where any one of the groups represented by I has a bond other than the bond represented by general formula (IV) and is linked. The effects of the present invention can be obtained even if this second bond is not broken during development. Examples of such combinations include, for example: A-(Ll) -B -1,2-DI "\-Next, the preferred range of the compound represented by the general formula (IV) will be described below. It is particularly effective when A represents a coupler residue. In the general formula (IV), A is the following general formula (Cp-/)
, (Cp--2), (Cp-3), (Cp-1, (Cp
-r), (Cp-g), (Cp-y), (Cp-♂),
When it is a coupler residue represented by (Cp-9), (Cp-70) or (Cp-//). These couplers are preferred because of their high coupling speed. General formula (Cp-/) General formula (Cp--2) Rsa -NH-C-CH-C-ho-R5□General formula (C
p-3) General formula (Cp-4t) General formula (Cp-r) General formula (Cp-a) General formula (Cp-7) General formula (Cp-♂) General formula (Cp-9) General formula (Cp -io) υ General formula (Cp-//) R60-CH-R51 In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group. In the above formula, R51, R52, R53, R54% R55%
R56SR57XR58% R59 rod R6G or R
When 61 contains a diffusion-resistant group, it means that the total number of carbon atoms is /~
3, preferably /θ~22, otherwise the total number of carbons is /! The following are preferred. Next, R51 of the general formula (Cp-/) to (Cp-//)
"'-'R51, !, m and pK will be explained. In the formula, R51 represents an aliphatic group, aromatic group, alkoxy group or heterocyclic group, and R52 and R53 each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by R51 preferably has 7 to 22 carbon atoms, is substituted or unsubstituted, linear or cyclic,
It may be either saturated or unsaturated. Preferred substituents for the aliphatic group include an alkoxy group, an aryloxy group, an amine group, an acylamino group, an aryl group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R51 are: isoprobyl, isobutyl, te.
rt-butyl group, isoamyl group, tert-amyl group,
/, /-dimethylbutyl group, /, /-dimethylhexyl group, /+/-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, comethoxyinpropyl group, λ-phenoxyisopropyl group, l- p-/tert-butylphenoxyimpropyl group, α-aminoinopropyl group, α-(diethylamino)inpropyl group, α-(succinimido)isopropyl group, α-(phthalimido)inpropyl group, α
-(benzenesulfonamido)isopropyl group, etc. When R51, R52 or R53 represents an aromatic group (particularly a phenyl group), 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 arylox group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. The aryl group may be further substituted with one or more alkyl groups having a total carbon number of 1-yss. The phenyl group represented by R51, R52 or RSa further includes an amine 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-carbon atoms. Alternatively, it may be substituted with a halogen atom. R51% R52 or R53 may also represent a substituent in which one phenyl group is fused to another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents. When R51 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 7 to 32 carbon atoms, preferably 7 to 2 carbon atoms. may be substituted with a halogen atom, aryl group, alkoxy group, etc. When R51 do. Such heterocycles include thiophene, furan,
Pyran, pyrrole, pyrazole, pyridine, pyrazine,
Examples include pyrimidine, pyritazine, indolizine, imidazole, thiazole, oxazole, trinodine, thiadiazine, and oxazine. These may further have a substituent on the ring. In the general formula (Cp-J), R55 is carbon number / to 3
2, preferably 1 to 22 linear or branched alkyl groups (e.g., methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g., allyl group, etc.), cyclic alkyl groups (e.g., cycloynthyl group, cyclohexyl group, norbornyl group), aralkyl group (e.g. jc-habenzyl, β-phenylethyl group nato), cyclic alkenyl group (e.g. cyclo is enthenyl,
cyclohexenyl group, etc.), and these represent a halogen atom, nitro group, cyan group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkylthiocarbonyl group, 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 may be substituted with a group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxyl group, mercapto group, etc. Furthermore, R55 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have seven or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyan group, aryl group, alkoxy group, aryloxy group, carboxyl 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, alkyl It may have an amino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group, etc. Furthermore, KR55 is a heterocyclic group (for example, a !-membered or ≦-membered heterocyclic group containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group,
furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic groups substituted with the substituents listed for the above-mentioned aryl groups, aliphatic or aromatic acyl groups, alkylsulfonyl groups, It may also represent an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, R54 is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having from 32 to 32 carbon atoms, preferably from 22 to 22 carbon atoms (these groups are substituted with the substituents listed above for 1'taa). ), aryl groups and heterocyclic groups (which may have the substituents listed above for R55), alkoxycarbonyl groups (for example, methoxycarbonyl groups,
ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group), alkoxy group (e.g., methoxy group), , ethoxy group 1, heptadecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.),
Alkylthio groups (e.g. ethylthio, dodecylthio), arylthio groups (e.g. phenylthio, α-
naphthylthio group, etc.), carboxy group, acylamino group (e.g. acetylamino group, j-[(,2゜darzy t
ert-amylphenoxy)acetamido]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylzolopionamide group, etc.), N
-arylacylamino groups (e.g. N-phenylacetamide, etc.), ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamino groups (e.g. phenylamino, N- methylanilino group, diphenylamino group, N-acetylanilino group, -ichiroro!-tetradecanamideanilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cyclo Amino groups (e.g., pyboridino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g., goupyridylamino group, copenzoxazolylamino group, etc.), alkylcarbonyl groups (e.g., methylcarbonyl group, etc.), arylcarbonyl groups (e.g. phenylcarbonyl group), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.),
Carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-7enylcarpamoyl, etc.), sulfamoyl group (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl group) , N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,
It represents any one of an N-diarylsulfamoyl group, a cyano group, a hydroxy group, and a sulfo group. In the formula, RSS is a hydrogen atom or a straight chain or branched alkyl group having 7 to 32 carbon atoms, preferably / to
It represents an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, which may have the substituents listed for RSS above. Further, R56 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R55 above. R56 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, or a ureido group. , urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N
-arylanilino group, N-alkylanilino group, N-
It may also represent an acylanilino group or a hydroxyl group. R57, R58 and R59 each represent a group commonly used in glue-equivalent phenol or α-naphthol couplers; specifically, R57 is a hydrogen atom,
Halogen atom, alkoxycarbonylamino group, aliphatic hydrocarbon residue, N-arylureido group, sulfamoyl group, sulfonamide group, acylamino group, -〇''62
or -8-R62 (however, R62 is an aliphatic hydrocarbon residue); when two or more R57s exist in the same molecule, the two or more R57s may be different groups; Group hydrocarbon residues include those having substituents. Furthermore, when these substituents include an aryl group, the aryl group may have the substituents listed for R5S above. Examples of RSS and R5'J include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom; Including those with substituents. Further, R58 and R59 may jointly form a nitrogen-containing heterocyclic nucleus. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. and preferably an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, L-butyl, inbutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.),
It is an alkenyl group (eg, allyl, octenyl, etc.). Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, quinolyl, chenyl, pyridyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, petro, alkoxy, Aryloxy, arylthio, arylthio, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl,
Examples include groups such as sulfonyl and morpholino. ! is an integer from 7 to q, m is an integer from / to 3, and p is an integer from / to ! represents an integer. R60 is an arylcarbonyl group, an alkanoyl group with a carbon number of λ to 3λ, preferably 2 to 22, an arylcarbamoyl group, an alkanecarbamoyl group with a carbon number of 2 to 32, preferably co-JJ, a carbon number of / to 32, preferably / ~22
represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent. Examples of the substituent include an alkoxy group, an alkoxycarbonyl group,
Examples include an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsuccinimit group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group. R61 is an arylcarbonyl group, an alkanoyl group having 2 to 3 carbon atoms, preferably 1 to 2 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 2 carbon atoms, and 32 carbon atoms. , preferably /~2
An alkoxycarbonyl group or an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group having a carbon number of /~32, preferably /~22. or t-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, a sulfur atom, such as a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group) ), and these may have the substituent described above for R60. Among the above coupler residues, yellow coupler residues include those in the general formula (Cp-/) in which R51 represents a t-butyl group or a substituted or unsubstituted aryl group, and R52 represents a substituted or unsubstituted aryl group. and in the general formula (-Cp--2), R52 and R53
It is preferable that represents a substituted or unsubstituted aryl group. Preferred magenta coupler residues are of the general formula (C
p-3>, R54 represents an acylamino group, a ureido group, or an arylamino group, and R55 represents a substituted aryl group;
When 56 represents a hydrogen atom, and the general formula (Cp-
R54 and R56 in t) and (CP-/-)
represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, cyclic alkenyl group, alkoxy group, ureido group, or acylamino group. A preferred cyan coupler residue has the general formula (Cp
-7) R5? But, the acylamino group or ureido group at the co-position,! When the position represents an acylamino group or an alkyl group, and the 6th position represents a hydrogen atom or a chlorine atom, and R57 in the general formula (Cp-9)! When R58 is a hydrogen atom, R59 is a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group. be. Preferred colorless coupler residues have the general formula (Cp
-10), when R57 represents an acylamino group, sulfonamide group or sulfamoyl group, and when R2O and R61 represent an alkoxycarbonyl group in the general formula (Cp-//), this is the case. Further, any part of R51 to R61 may form a bis-form or higher polymer, and a heptad polymer or a non-bis polymer having an ethylenically unsaturated group in any part of these groups may be formed. It may also be a copolymer with a color-forming monomer. Preferred ranges will be explained below when A in general formula (IV) is represented by general formula (V). When P and Q represent a substituted or unsubstituted imino group, preferably an imino group substituted with a sulfonyl group or an acyl group. At this time, P and Q are expressed as follows. General formula (N-/) General formula (N-2) where the black mark represents the bonding position with A1 or A2, and the Kaoru yellow mark indicates the bonding position with one of the free bonds of -(x=y← In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (for example, a methyl group). , ethyl group, benzyl group, phenoxybutyl group, inpropyl group, etc.), substituted or unsubstituted aromatic groups with a carbon number of ~/θ (e.g. phenyl group, comethylphenyl group, 1-f-butyl L<t -dodecyloxyphenyl group, etc.), or a q- to 7-membered heterocyclic group selected from a sulfur atom, a sulfur atom, or an oxygen atom as a hetero atom (e.g. -1pyridyl group, /-phenyl-Q-imidazolyl group) , -furyl group, benzothenyl group, etc.). When A1 and A2 represent a group that can be removed by an alkali (hereinafter referred to as a precursor group), preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. , a hydrolyzable group such as a carbamoyl group, an imidoyl group, an oxacyl group, a sulfonyl group, U.S. Pat. U.S. Pat. No. 310,612, U.S. Patent No. J, 474, U.S. Pat.
t, 4t7/issue, 3,932° 4tgo issue or 3,993. The precursor group described in At No. 1 causes the anion to transfer electrons through a conjugated system, thereby causing the cleavage reaction, and the precursor group described in U.S. Pat. Precursor group or U.S. Patent &, 363
, /Bu No. 1, No. 4T, and No. 4T No. 10.411, precursor groups using imidomethyl groups are mentioned. In general formula (V), preferably P represents an oxygen atom and A2 represents a hydrogen atom. More preferably, in general formula (V), except when X and Y are methine groups having -(L1?B+L2nd DI as a substituent), the other X and Y are substituted or unsubstituted methine groups. Among the groups represented by the general formula (V), particularly preferred ones are represented by the following general formula (M) or (■): General formula (Vl) General formula (■) /AI In the formula, The arrow is +L l+ -B + L2) -D
Represents the V W position to which I is bonded, and P, Q, A1 and A2 are general formula (V)
, R represents a substituent, and q represents an integer from θ to 3. When q is 2 or more, two or more R may be the same or different,
When two R's are substituents on adjacent carbon atoms, it also includes the case where they form a divalent group and are connected to form a cyclic structure. In that case, a be/yne fused ring, such as 7talenes,
Benzonorbornenes, chroma/classes, a/)"-h classes,
Benzothiophenes, quinolines, hensifurans, 2
, 3-dihydrobenzofurans, indanes, or indenes, which may further have 7 or more substituents. Preferred examples of substituents when these fused rings have substituents, and preferred examples of R when R does not form a fused ring are listed below. That is, aliphatic groups (e.g. methyl, ethyl, allyl, benzyl, dodecyl), aromatic groups (
(e.g. phenyl group, naphthyl group, leaf enoxycarbonylphenyl group), nitrogen atom (e.g. chloro atom, pro-7 atom), alkoxy group (e.g. methoxy group, hexadecyloxy group), alkylthio group (e.g. methylthio group, dodecylthio group) group, benzylthio group), aryloxy group (e.g. phenoxy group, <1-1-octylphenoxy group, !, 4t-di-t-amylphenoxy group)
, arylthio group (e.g. phenylthio group, q-dodecyloxyphenylthio group), carbamoyl group (e.g. N
-ethylcarbamoyl group, N-hexadecylcarbamoyl group, N-3-(J,<t-di-t-amylphenoxy)furobylcarbamoyl group, N-methyl-N-octadecylcarbamoyl group), alkoxycarbonyl group (
For example, methoxycarbonyl group, 2-cyanoethoxycarbonyl group, ethoxycarbonyl group, dodecyloxycarbonyl group, 3-(di-t-amylphenoxy)phenoxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, cnonylphenoxy carbonyl group), sulfonyl group (e.g. evamethanesulfonyl group, benzenesulfonyl group, P-)luenesulfonyl group), sulfamoyl group (e.g. N-propylsulfamoyl group, N-methyl-N-octadecylsulfamoyl group) , N-phenylsulfamoyl group, N-dodecylsulfamoyl group), acylamino group (e.g. acetamido group, benzamide group, tetradecaneamide group,
a-(J, 4t-di-t-amylphenoxy)butanamide group 1.2-(z, 4t-di-t-amylphenoxy)butanamide group, J-(, z, <t-di-t-amylphenoxy ) tetradecaneamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, hexatecylsulfonamide group), acyl group (e.g. acetyl group, benzoyl group, myristoyl group, valmitoyl group), nitrone group, acyloxy group (
For example, acetoxy group, benzoyloxy group, lauryloxy group), ureido group (e.g. 3-phenylureido group, 3-(4t-cyanophenylureido group), nitro group, cyano group, heterocyclic group (nitrogen atom as a petro atom) , a q- to 6-membered heterocyclic group selected from an oxygen atom or a sulfur atom, such as a nafuryl group, a copyridyl group, a noimidazolyl group, a /-morpholino group), a hydroxyl group, a carboxyl group, an alkoxycarbonylamino group (
For example, methoxycarbonylamino group, phenoxycarbonylamino group, dodecyloxycarbonylamino group),
Sulfo group, amino group, arylamino group (e.g. anilino group, coumethoxycarbonylanilino group), aliphatic amine group (e.g. N,N-diethylamino group, dodecylamino group), sulfinyl group (e.g. sulfamoylamino group (e.g. 3-phenylsulfamoylamino group), thioacyl group (e.g. thiobenzoyl group), thioureido group (e.g. 3-phenylthioureido group), heterocyclic thio groups (e.g. thiadiazolylthio group), imide groups (
Examples include succinibado group, 7-thallimide group, octadecenylimide group) and heterocyclic amino groups (eg, q-imidazolylamino group, 9-pyridylamino group). When there is an aliphatic group in the partial structure of the above substituent, the number of carbon atoms is 7 to 32, preferably /~coO, chain or cyclic, straight chain or branched, saturated or unsaturated, substituted or unsubstituted. It is a substituted aliphatic group. When there is an aromatic group in the partial structure of the substituent listed above, the number of carbon atoms is 6 to 10, and it is preferably a substituted or unsubstituted phenyl group. The group represented by B in general formula (IV) is preferably one represented by general formula (B-/). In the general formula (B-/), P preferably represents an oxygen atom, and Q preferably represents an oxygen atom or one represented below. Here, the yellow mark represents the bond bonding to (X'=Y')n, and the -X-+ mark represents the bond bonding to A2. In the formula, G has the same meaning as explained in the general formulas (N-/) and (N-co). Furthermore, when the group represented by B in general formula (IV) is represented by the following general formula (B-2) or (B-3), it is particularly preferable in view of the effects of the present invention. General formula (B-2) General formula (B-3) In the Kaoru formula, the mark represents the bond bonding to A-(Ll)-, and the Kaoru mark represents the bond bonding to -(R2) -DI R, q, Q and A2 have the same meaning as explained in the general formula (M) or (■). In the general formula (IV), a preferable example of DI is a 1-aromatic substituted tetrazolylthio group (the aromatic group preferably has a carbon number of g to /θ),! - an aliphatic substituted tetrazolylthio group (the aliphatic group preferably has a carbon number of / to /θ) and a benzotriazolyl group. These may have a substituent, and the substituent is selected from those listed for R in general formulas (M) and (■). In the general formula (F/), both V and W are preferably 0. The group represented by A in general formula (IV) is particularly preferably a coupler residue. Further preferred embodiments of the present invention will be described below. The compound contained in the red-sensitive emulsion layer is a coupler residue represented by the general formula (IV) in which A is represented by the general formula (Cp-7>, (Cp-♂), (Cp-9)t or (Cp-/θ). A preferred example is when it is a group. Examples of compounds and synthetic methods of the compound represented by general formula (I) are described, for example, in the documents listed below. That is,
Tokukai Sho 0-/1j9jθ, Tokukai Sho≦O-7! θ<to
No. 0-72379, No. 40-7232/, No. 0-/ko/ko♂! No. 6θ-2/θ73, No. 0
It is described in No.-770/K or %Kai-Sho 60-K θ39G No.3. Next, the compounds represented by general formulas (II) and (I[l) will be described in detail below. Examples of the aromatic group represented by R1 include substituted or unsubstituted aromatic groups in which the aromatic residue has 2 to 3 Q carbon atoms. Examples of the aliphatic group represented by R3 include substituted or unsubstituted aliphatic groups in which the aliphatic residue has 7 to 3[theta] carbon atoms. Examples of the heterocyclic group represented by R1 include substituted or unsubstituted heterocyclic groups in which the heterocyclic residue has 2 to 30 carbon atoms. R2 represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and examples include a halogen atom, a hydroxy group, an amine group, a carboxyl group, a sulfonic acid group, a cyan group, an aromatic group, and a heterocyclic group. , carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic Examples include a group sulfonyl group, a sulfamoylamine group, a nitro group, an imide group, and the number of carbon atoms contained in R2 is θ to 30. - R2
Examples of cyclic R2 include a dioxymethylene group. Z2 represents O, S or R4N, and R4 represents hydrogen or a heptavalent group. The heptavalent group is preferably Rlo(Za)-(■) represented by the following general formula (■), where z3 represents CO or SO□, d represents zero or /, and Rlo is Represents a hydrogen atom, an aliphatic group having up to 30 carbon atoms, an aromatic ring group having up to 30 carbon atoms, or a hydrogen atom.1. / R11 and R1 in NR11R12
2 may be the same or different. In R10, R11 and R1 of -NR11R12
2 may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.). zl represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include -rogen atom, -0R13, -0CR13
, -NH8O2R13. Further, heterocyclic groups (succinimide group, phthalimide group, hydantoinyl group, pyrazolyl group, cobenzotriazolyl group, etc.) which are connected to the coupling active position of the coupler through a nitrogen atom can be mentioned. Here, R13 represents an aliphatic group having 1 to 3θ carbon atoms, an aromatic group having ≦30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. D is a carbon number ~20 aromatic group or a carbon number ~20
represents a heterocyclic group. In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, linear, branched, or cyclic,
Typical examples include methyl group, ethyl group, hydroxyethyl group, butyl group, cyclohexyl group, allyl group, propargyl group, methoxyethyl group, n-7' syl group, n-
Dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl L, 2. &-G tert-amylfenokidib. Pyr group, 2. 'l-di-tert-amylphenoxybutyl group, etc. are included. Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, naphthyl group, tolyl group, 2-tetradecyloxyphenyl group, hantafluorophenyl group, <t-tert-octylphenyl group, 2
-Chloro-5-)"f syloxycarbonylphenyl group, cuchlorophenyl group, coumethoxyphenyl L &
-Hydroxyphenyl group, etc. In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include λ-pyridyl group, gouhy9yl group, 2-furyl group, gouchenyl group, quinolinyl group, q
-pyrazolyl group, etc. Preferred examples of substituents are explained below. R1 is preferably an aromatic group, particularly preferably a phenyl group or a naphthyl group. Preferred substituents for aromatic groups include alkoxy groups (e.g., tetradecyloxy group, methoxy group), alkoxycarbonyl groups (e.g., dodecyloxycarbonyl group, methoxycarbonyl group), acylamino groups (e.g., gu(, 2,4t-tert), -amylphenoxy)butanamide group, tetradecanamide group), sulfonamide group (e.g. hexadecylsulfonamide group), sulfamoyl group (e.g. 3-(,Z. , N, N-diethylsulfamoyl group, hexadecylsulfamoyl group), carbamoyl group (eg id'dodecylcarbamoyl group, <'-(co, 4
t-di-tjrt-amylphenoxy)butylcarbamoyl group), imide group (e.g. dodecylsuccinimide group, octadecenylsuccinimide group), sulfonyl group (
For example, dodecylsulfonyl group, furopanesulfonyl group,
methanesulfonyl group), aliphatic thio groups (eg, dodecylthio group, ethylthio group), halogen atoms, cyano groups, aliphatic groups (eg, methyl group, t-butyl group), and the like. Regarding R2, a and b, it is most preferable that a = b = θ, and then &==/ or b=/, where R2 is a halogen atom, an aliphatic group (e.g. methyl group, ethyl group, t-
octyl group), acylamino group (e.g. acetamido group, butanamide group), sulfonamide group (e.g. be/ynesulfonamide group, methanesulfonamide group), alkoxyacylamino group (e.g. ethoxycarbonylamino group, imbutoxycarbonylamino group) ) are preferred examples. Examples of the aliphatic group represented by R3 include a methyl group, a propyl group, a butyl group, a tert-butyl group, a pentyl group, a tridecyl group, and cases in which these groups have a substituent. Preferred substituents for aliphatic groups include aromatic oxy groups (e.g. co, tert-amylphenoxy group, co, tert-hexylphenoxy group, λ, 4t-tert-octylphenoxy group, aliphatic oxy groups (e.g., methoxy, ethoxy, dodecyloxy, hexadecyloxy), sulfonamide groups (
Examples include methanesulfonamide group, goomethylbenzenesulfonamide group), and the like. A preferred Z2 is R4N, where R4 is -C
OR1o (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, ktafluoropenzoyl group, p-chlorobenzoyl group, etc.)
, -COORlt (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -8O2R1G (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group) group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group, etc.), -CONR11R12 (N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group,
N,N-dipylcarbamoyl group, morpholinocarbonyl group, pi is lysinocarbonyl group, tercyanophenylcarbonyl L 3+''-dichlorophenylcarbamoyl group, gumethanesulfonylphenylcarbamoyl group), -8O2NR1IR12 (N,N-dimethylsulfur group) moyl group, N,N-diethylsulfamoyl group, N.N-dipropylsulfamoyl group, etc. Particularly preferred z2 are -COR1o, -COOR11 and -5O2R1o. Here, R11, R, 2 has the same meaning as above. Preferred examples of zl include a hydrogen atom, a halogen atom, an aliphatic oxy group, and an aromatic oxy group. Couplers represented by general formulas (I), (II) and (Ill), Among them, the couplers represented by the general formulas (II) and (DI) may form a dimer or a multimer of more than two molecules bonded to each other via a covalent group or a group having a valence of two or more in the substituent. In this case, the carbon number range shown above for each substituent may be outside the specified range.If the coupler represented by the general formula above forms a multimer, addition polymerization with a cyan dye-forming coupler residue is possible. A typical example is a single or copolymer of an ethylenically unsaturated compound (cyan color-forming monomer).In this case, the polymer contains repeating units of the general formula (IK) and has a cyan color-forming monomer represented by the general formula (DO). More than one type of repeating unit may be contained in the polymer, and R13 is a hydrogen atom and carbon number 7 in the co-electrochemical formula containing seven or more types of non-color-forming ethylene-like polymers as a copolymerized acid. -9 alkyl groups or chlorine atoms, E represents -CONH-. -COO- or a substituted or unsubstituted phenylene group, G represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, T is -CONH-
, -NHCONH-, -NHCOO-. -NHCO-, -0CONH-, -NH-, -COO-
. -0CO-, -CO-, -0-, -8O2-, -NH8
Represents O2- or -502NH-. RgS t is 0
or / indicates. QQ represents a cyan coupler residue from which a hydrogen atom has been removed from the compounds represented by formulas (n) and (I). As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of general formula (IX) and a non-color-forming ethylene-like monomer described below is preferred. Examples of non-color-forming ethylene-like monomers that do not couple with oxidation products of aromatic-grade amine development systems include acrylic acid,
α-chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, Methylenebisacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-
octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate),
Vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateril, aromatic vinyl compounds (e.g. styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itacon acids, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and co- and he-co-vinylpyridine. . Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more of the non-color-forming ethylene-like monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used. As is well known in the art of polymer couplers, when containing a repeating unit of the general formula (DO), a non-color-forming compound copolymerized with an ethylene-like monomer having a cyan dye-forming residue of the present invention is used to form it. The ethylene-like monomer favorably influences the physical and/or chemical properties of the copolymer formed, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility, thermal stability, etc. The cyan polymer coupler used in the present invention (a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the general formula (■) above) can be selected to It may be made by emulsifying and dispersing gelatin in an aqueous solution in the form of a neutralized latex, or it may be made by direct emulsion polymerization.A lipophilic polymer coupler is emulsified and dispersed in an aqueous gelatin solution in the form of a latex. The method is described in U.S. Pat.
t1/, No. 220, and U.S. Patent No. θ10,2//, No. 3°320.9! You can do this by using the method described in item C. General formula (I) and (If) or (III) of the present invention
The compound can be used primarily for sharpness enhancement, multicolor photographic materials having at least three different spectral sensitivities on a support.
It can be applied to improve sensitivity and color reproducibility. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be selected arbitrarily as required. The compounds of the present invention are used in the red-sensitive emulsion layer or its adjacent layer. Further, the compound of the present invention can be used in any layer such as a high-speed layer, a low-speed layer, or a medium-speed layer, and can also be used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto. The amount of the compound of the general formula (R) varies depending on the structure of the compound, but is preferably from /xIQ-6 to θ.5 mol,% per mole of silver present in the same layer or adjacent layer, preferably lx/θ- 5 to /X/θ-1
It is a mole. The amount of the compound of general formula (It) or (III) to be added varies depending on the structure of the compound, but is preferably /x/θ-5 to 1 mol per mol of silver present in the same layer or an adjacent layer, particularly preferably /x /θ-4 to 0°1 mole. The molar ratio of the compound of general formula (I) and the compound of general formula (II") or general formula (SIN) is (I)/(It) or (I) = (θ, θ//9, 9) ~(!o/lo
) Preferably (I)/(II) or (III)=(/
/9t) to (3o/7o). (Compound Examples) Specific examples of the compounds of the present invention are listed below, but the invention is not limited thereto. Example of compound of general formula (I) (I 0H (j) (go) (/l) (/su (lj) (2θ) 2H5 L2.2) 2H5 (,23) (, z4t) to=N (koj) (koro) h (core) (ko/) to 285 CH2CH2C0□CH2CF3 (3h7 α 2MS (3r) (g/) (4t3) (guri (&4) (q7) 2H5 The following are preferable examples of monomers used as polymer couplers. (4tr) Compound examples represented by general formula (II) and general formula (III) (jo) 02H (!2) (!3) ( j4t) (Evening(!6) (!7) CH2C00c12H25 (!♂) (!9) (niO) (nil) (Go2) (≦3) (tsu(6t) (≦9) Shifi3 ShiU”fi (Xfi2UIJ2MH x : y= gθ 4to (molar ratio) x:y=<<θ
:60 (mole ratio) In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, silver halide, such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride, is added. The preferred silver halide that may be used is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Preferred for horse chestnuts is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide. The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used. The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, by Research Disclosure Co., Ltd.
RD), No. 17643 (December 1978), 22
-23rA,'I, Emulsionpreparation
The photographic emulsion used in the present invention can be used in accordance with the method described in "Physics of Photography" and "Physics of Photography "Chemistry", published by Paul Montell (P. Glafkides, Cbimie eL r'l+
ysique I'l+otogral]l+1que
1'aul Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Cal Press (C0F,
Duffin+r'l+oLo-Hrapl+ic
E+1ulsion CI+emistry (Fo
cal PresSs 196G), "Manufacture and Coating of 1° Photographic Emulsion" by Zelikman et al., published by Focal Press (
V, L, 2elikman eLal, MnkiB a
ndCoatinI? Yen + oto8raphic
lE+oul-s, ion, Focal Pres
It can be produced using the method described in, for example, S.S., 19 G 4 ). 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. Method for forming good 0 grains under excess silver ions (
A so-called back mixing method) can also be used. As a type of simultaneous mixing method, p in the liquid phase in which silver halide is produced is
It is also possible to use a method in which A g is kept constant, ie the so-called Chondrald-Gupljet method. 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 combined and used. The silver halide emulsion consisting of the regular grains described above can be obtained by controlling p to g and pi-1 during grain formation. For more information, please refer to 7 otographic science and engineering (I'l+ojogra).
pbic 5science and Engineer
iB) Volume 6, pp. 159-165 (I962); Journal of 7i) Graphic Science (Jour
nal of yen+oLogrnpl+ic 5cie
nce)*12, pages 242-251 (I964), US Patent No. 3.055,394 and British Ney; For llj dispersion 7L cutting, an emulsion containing average grain i (silver halide grains with a C diameter larger than about 0°1 micron, at least about 95% of which is within ±40% of the average grain diameter) is used. Typically, the average particle diameter is approximately 0.2
5 to 2 microns and at least about 95% or i
Emulsions having at least about 95% of the silver halide grains within ±20% of the average grain diameter can be used in the present invention. Methods for making such emulsions are described in US Pat. No. 3,574,828, US Pat. No. 3,655,394 and British Patent No. 1,413.748. Also, JP-A-48-8600, JP-A-51-39027,
51-[13097, 53-137133, 54 48521, 54-99419, 58
Monodisperse emulsions such as those described in No. 37635 and No. 58-49938 can be preferably used in the present invention. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. The tabular grains are 〃)7M, 7
Autographic Science and Engineering (G:uto[+I'boLoHrapbicSc
engineering), 1st
Volume 4, pages 248-257 (1970); US Patent! l
I's4,434. , No. 226, 4,414.31
(No. I, No. 4,433,048, No. 4,439,52
0 and British Patent No. 2.112.157. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness.
This is described in detail in U.S. Pat. No. 4,434.22G, cited above. The crystal structure may be uniform, or the inside and outside may have different halogen compositions. These emulsion grains may have an M-shape (Iη structure).
1) No. 27,146, U.S. Patent No. 3.505.0138
No. 4,444.11177 and patent application No. 1982-2
No. 48469 and the like. Furthermore, silver halides of different compositions may be bonded by epitaxial bonding, or may be bonded with compounds other than silver halide, such as silver oxide and lead oxide.These emulsion grains are disclosed in the US Pat. No. 4.094.684, same 4,
No. 142,900, No. 4,459,353, British Time F
r No. 2°030.792, U.S. Patent No. 4.349. (
i22, 4,395.478, 4 + 433
．． No. 501, No. 4,403.007, No. 3.65G,
9G2 No. 3,852. OG7, special 1311 1982
-Disclosed in IG2540 etc. It is also possible to use a mixture of grains of various crystal forms.The emulsion of the invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Are additives used in such processes subject to research disclosure? -No, 1
No. 7, No. 43 and No. 111716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and their locations are shown in the table below. 1h+nQJ1'QM 1(I)1764:l
I(01871(il) If to chemical sensitization 2
:1 page 648 page right column 2 Sensitivity 1 cut
Same as above 3 Spectral sensitizer, pages 23-24 6
Page 48 right column ~ Super sensitization page 649 Right column 4 Brightening agent Page 24 5 Anti-star glare agent Page 24-25 Page 649 Right column; Stabilizer 6 Light absorber 7 25~ Page 26 649 Right Kyo ~ Ilter Dye +3507. E491 Ultraviolet absorber 7 Anti-stain agent Page 25 right column G50 'g' (left ~
Right column 8 Dye image stabilizer page 25 9 Hardener page 2G (i51 page left column 10
Bangu 2600 Same as above 11 Plasticizer, lubricant 27 pages (i50 right 12 coating aid, Table 26
~Page 27 Difacet activity; IQ 13 Static protection Page 27. Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure
RD) No. 17643, ■-c~C; and the six pigment-forming power pullers described in this patent include the three primary colors of the subtractive color process (i.e., yellow, agenta Ij
11n is required for the coupler which can be developed by color development, and is a diffusion-resistant, 4-equivalent or 2-equivalent coupler.
'1: For the body side, in addition to the couplers described in the patents described in RD17+343, ■-C and D, the following are preferably used in the present invention. A representative example of the yellow coupler that can be used in the present invention is a hydrophobic 7-syl acetamide coupler having a ballast group. A specific example is US Patent R52
．． 407.210, Oyohi No. 2,875.057 Oyohi No. 13,2 G 5.506, etc.
The use of two-equivalent yellow couplers is preferred for the present invention, U.S. Pat.
No. 928, No. 3.933,501 tjJ: (71
Mm4tO22,620, etc., patents fi4,401.752, fi4.32 (3,024), RD18053 (I979)
), British Patent No. 1,425,020, West German Publication No. 2,219.917, West German Patent No. 2,201,361
No. 2.329,587 and: jS2,43
The S1 atom separation type yellow coupler described in No. 3,812 etc. is cited as a typical example. The α-benzoyl7ceto7nylide coupler provides a high color development of 12 degrees. The magenta couplers used in the present invention include hydrophobic ingzolone or cyano 7
Examples include cetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers. The 5-pyrazolone coupler is preferably a 2-pyrazolone coupler in which the 3-position is directly substituted with a 7-lyl 7-mi7 group or an acylamino group from the viewpoint of the hue of the coloring dye and the density of the coloring agent. 2
, No. 311.082, No. 2 + 343 e 703
No. 2, GOo, No. 788, f52,908,5
No. 73, 14 No. 3 sOG No. 2,653, No. 3 m 1
No. 52189 G and No. 3.930.015 of the same. As a leaving group for the 5-pyrazolone coupler of J4, US t-' is allowed as No. 4.310.01.
Nitrogen 71 described in No. 9; [child leaving group or US 1.
Particularly preferred is the t-arylthio plant described in 1st edition No. 4.351.897, and European 1st edition, i9 No. 73. (33
The 5-pyrazolone coupler having a ballast group described in No. 6 provides a high color density. Pyrazoloazole Kab5-Lytel, USA'vt Approval No. 3.3 G 9.
879, preferably the pyrazolobenzimidazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (I984) Year 6
24230 (June 1984) and JP-A No. 33552 (June 1984) and JP-A No. 33552 (June 1984)
Pyrazolo l 1 * 5-bJL described in US Pat. 1-2. 41F117V-L is particularly preferred. As cyan couplers used in the present invention, there are hydrophobic and diffusion-resistant 7Tall-based 7E/-L couplers. U.S. Pat. No. 2,474.293, preferably U.S. Pat. No. 4,05
No. 2,212, m4+14 (S, 39 (No. 5, No. 4)
Typical examples include the oxygen atom dissociation type two-element 7-toll couplers described in , 228.233 and 4.296,200. Further, specific examples of phenolic couplers are described in U.S. Patent No. 2,3G9,929, U.S. Pat. There is. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof includes an alkyl group higher than ethyl group at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772.002. 71/-le series cyan coupler having US Patent fjS2,772. IG
No. 2, No. 3.7513.30JL8, No. 4,1
26.39 (No. 3, No. 4.3 J 4' +011, No. 4,327.173, West German Patent No. 3,32
9,729 and European Patent No. 121°365, etc., the 2,5-diacylamide/if-converted phenolic coupler insertion ÷4 U.S. Patent f53°440.62
No. 2, No. 4,333.999, No. 4,451,5
No. 59 and No. 4,427,767, etc. i1i
! In order to correct the unnecessary absorption of the phenylureide color complex at the 2-position, it is preferable to use a colored coupler in combination with a color photosensitive material for photographing to perform mass A.
U.S. Patent No. 4.1 (No. 33,670 and Japanese Patent Publication No. 1987-
Yellow-colored magenta couplers described in US Pat. No. 39413, etc. or U.S. Pat.
Typical examples include the magenta-colored cyan couplers described in No. 38.258 and British Patent No. 1.14G, 368. Other colored couplers are listed in 1 above.
1D17G43, ■~ is described in Section 1. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
US Patent No. 4.3 G G, 237 and UK 1. +
L+ of magenta coupler in f license i2,125,570
This example is also described in European Patent No. 96,570 and German Application No. JS 3,234,533 as a yellow, magenta or cyan coupler. 'f special coupler is
A typical example of a polymerized dye-forming coupler that forms a two-way chain or higher polymer and is good at one-ζ is the US Nephrase. Yu:jS3
, 451.320 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Pat. No. 4,307,282. Couplers that release a photographically useful fl group upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is il? RD17G mentioned in i
43, 1,! described in sections ■~F. This coupler is useful. Part B, which is preferable in combination with the present invention, is JP-A-57-
Current liquid deactivated type represented by No. 151944; US patent:
jS4, 248.962 and JP-A-57-1542
Timing type represented by No. 34; Patent application 1987-: (
905: (This is a reaction type represented by No. 905, and a particularly preferred one is JP-A-57-151944, r13J 5
B-2179:12, Patent Application No. 1987-75474,
No. 59-82214, No. 59-82214 Ogami V1
Tsukasa 59-9 (Developer deactivated type DIR coupler described in I438 etc. and reactive type DIR coupler described in Japanese Patent Application No. 59-39653 etc.). Couplers which imagewise release nucleating agents or development accelerators or precursors thereof may be used in GB 2,097,140, ff12.
, No. 131.188. Particularly preferred are couplers that release a nucleating agent that has an adsorption effect on silver halide.
157638 and 59-170840. Suitable supports for use in the present invention include, for example, the R
D, No. 17043, page 28 Same as above, No. 187
1 [) from the right column on page 647 to the left column on page 648. The color photographic material according to the present invention can be developed by the conventional method described above. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment. In the washing process, it is common to use two or more jets of water to save water. As for stable housing 31, 1. In the case of a zero-line process, a typical example of which is multi-stage countercurrent stabilization treatment as described in TE 57-8543, 4th is required in the direction i of 2 to 91 fl. During the zero-line stabilization m, For the purpose of stabilizing the image? )+ffl compound is added 6. Adjust the membrane pH (e.g. Rt1
3-8) various buffering agents (e.g., borates, metaborates, borax, phosphates, carbon RIM, potassium hydroxide,
Typical examples include sodium hydroxide, 7-monodi7-hydromonocarboxylic acid, nocarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners may be added as needed (no phosphoric acid, aminopolycarboxylic acid, phosphoric acid, aminopolyphosphonic acid,
Various additives such as phosphonocarboxylic acid, etc.), pyrocides (penzoisonazolinone, iliti-7zolone, 4-thiazolinebenzimidazole, halogenated phenol, etc.), surfactants, optical brighteners, hard 11 odorants, etc. or two or more of the same or different target compounds may be used in combination. Also, the film 111 after treatment! It is preferable to add 11 ammonium salts such as ammonium chloride, ammonium nitrate, GATnl 17 ammonium, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as regulators. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or motion pictures, color reversal film for slides or television, color paper, color blank film, and color reversal vapor. -17123 (I000
It can also be used in black-and-white light-sensitive materials using a mixture of three-color couplers, as described in J. [Example] Hereinafter, the present invention will be specifically explained with reference to Examples. Example/ A multilayer color photosensitive material consisting of each layer having the composition shown below on a cellulose triacetate film support as a sample/
/It was created. 1st layer; antihalation layer black colloidal silver ・・・・・・・・・・・・ 0. ／♂
g/m2 Ultraviolet absorber C-i...0. /4
g/m2 UV absorber C-co...0.77
Gelatin layer 2nd layer containing g/m2; Intermediate layer compound H-/ 0
．． 72g7m2 natural silver bromide emulsion (7 moles of silver iodide, average grain size θ, 07μ)...
・・Silver coating amount (same below) 0, /! Gelatin layer containing g/m2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・ 0.
72g/m2 (6 moles of silver iodide, average grain size 0.j
μ) Sensitizing dye I ・・・・・・・・・7.0×/θ−5 mol sensitizing dye ■ ・・・・・・・・・・・・ Silver 2.0×/θ-5 moles of sensitizing dye per 1 mole ■・・・・・・・・・λ, /×/θ-4 moles of sensitizing dye ■・・......2.0x/θ-5 mole coupler C-3 for 1 mole of silver...0.30g
/m2 coupler C-e ・・・・・・・・・・・・0
．． 0/g/m2 coupler C-t ・・・・・・・・・
...0. Gelatin layer containing Ot1g/m2 Second red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
... /, 2g/m2 (silver iodide 10 mmol average grain size 7.2μ) Sensitizing dye■ ......
12 to 1 mole of silver! , koX10-5 mol sensitizing dye■ ・・・・・・・・・・・・For 1 mol of silver/, j×/θ-5 mol sensitizing dye■ ・・・・・・・・・...λ for 7 moles of silver, / x 70-4 mol sensitizing dye ■ ......... /, jXlo-5 mol for 1 mole of silver Coupler C-t .・・・・・・・・・θ, J
Jg/m2 coupler C-a・・・・・・・・・・・・
・0.0/g/m2 coupler C-r...
...0. Gelatin layer 5th layer containing OIItg/m2; 3rd red-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・・・・
...2.0 g/m2 (10 moles of silver iodide, average grain size /, /μ) Sensitizing dye■ .........J, j x 10- for 1 mole of silver S mole sensitizing dye■ ・・・・・・・・・・・・For 1 mol of silver/, B×10-5 mol sensitizing dye■・・・・・・・・・・・・1 silver Co, Co × 1 o-s mole per mole Sensitizing dye■・・・・・・・・・・・・・・・tXlo-5 mole coupler C−t・・group・・-0, /Og
/m2 Coupler C-7......Ooozag/m2 containing gelatin Jim 6th layer; Intermediate layer compound H-7......0. 02g
/m2 gelatin layer second layer; first green-sensitive emulsion layer silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
θ, j! g/m2 (Silver iodide! Morti, average grain size O, 4tμ) Sensitizing dye ■・・・・・・・・・
...3 for 1 mol of silver, ♂×/θ-4 mol sensitizing dye■ 3 for 1 mol of silver
．． 0X10-5 molar coupler C-/ 0.29
g/m2 coupler C-9・・・・・・・・・・・・0
．． 04tg/m2 coupler C-/θ・・・・・・・・・
・0.0<Ig/m2 coupler C-a...
Old: 1st gelatin layer containing θ, 0/g/m2; 1st green-sensitive emulsion layer Silver iodobromide emulsion...
... /, 0g7m2 (silver iodide 10 moles, average grain size /, λμ) Sensitizing dye V・・・・・・・・・・・・λ, 7×IQ-4 moles increase for 7 moles of silver Sensitive dye ■・・・・・・・・・λ, /×/θ-5 mol coupler C-//・・・・・・・・・0.04tg/ for 1 mol of silver
m2 coupler C-e ・・・・・・・・・o, 002
g/m2 coupler C-/, 2 ・・・・・・・・・0
．． 07g/m2 coupler C-70...0.0
0! Gelatin layer 9th layer containing g/m2; 3rd green-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
... /, jg/m2 (10 moles of silver iodide, average grain size /, ♂μ) Sensitizing dye V・・・・・・・・・1 mole of silver

[3.0 x 70-4 mole sensitizing dye for 1 mole of silver 2, g x 70-5 mole coupler for 1 mole of silver C-//... ...0. θJg/
m2 coupler C-/θ---- 0.00jg/
Gelatin layer containing m2 1st O layer; yellow filter layer, yellow colloidal silver 0.
θ4tg/m2 coupler C-9・・・・・・・・・・・・
...o, 10g/m2 compound H-7...
・・・・・・ Gelatin layer 1/layer containing 0.20 g/m2; 1st back emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・0
．． 32g/m2 (silver iodide! Morch, average grain size 0.
3μ) Coupler C-/3...0. A♂
g/m2 coupler C-<t ・・・・・・・・・・・・
・12th gelatin layer containing 0.03 g/m2; 1st green-sensitive emulsion layer silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
0.29 g/m2 (silver iodide 10 moles, average grain size o, rμ) coupler C-/3...
0. Gelatin layer containing λ2 g/m2 73rd layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・・・・・・・
0.79 g/m2 (silver iodide/q mole, average grain size/,/μ) Sensitizing dye ■ 2.3 x 10-4 per 7 moles of silver Mol coupler C-/3...0.19g7m
Gelatin layer 11.2 containing gelatin layer 11. Layer: 1st protective layer UV absorber C-/...0.20g/m2
Ultraviolet absorber C-,2...0.90g/m2
Gelatin layer 1st layer containing] 2nd protective layer polymethyl methacrylate particles (diameter/, jμ) 0. Ojg/m2
In addition to the above composition, each gelatin layer containing 1 gelatin hardening agent C-1t,
t and a surfactant were added. The sample prepared as described above was designated as sample //. The compounds used to prepare the samples are shown below. C-3 (conventional cyan coupler) C-4t (coupler described in U.S. Pat. No. 9,291.962) -t OU)12(,'H2SO2CH3 C-7 C-♂ CH3 -9 α C-/ / C-/λ α α C-i<t (CH2=CH8O2CH2CONHCH2iH- as sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ 2H5 Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sample // A sample prepared in exactly the same manner as sample // except that the coupler in the red-sensitive emulsion layer was changed as shown in table/.
- ~ // Closed. Coupler structures used in comparative examples C-7t (DIR coupler described in U.S. Pat. No. 4t, 4109, J, 2J) C-/l (Described in U.S. Pat. No. 11,4t2/, ♂<tj) Certain DIR couplers) C-/7 (DIR couplers described in U.S. Patent No. , cyan coupler described in Wata No. 9) The obtained sample //~/l was subjected to wedge exposure, and the following color development treatment was performed.
"7G removal and spray washing 22-3" seconds Color development Da/,/-1:0. / 3 minutes■
Stop 22-3/30 seconds ■ Wash with water -2-3/30 seconds ■ Bleach
3♂±/ 3 minutes■Washing 27~3//minute■Fixing 3/±/
■Water wash -7~3/
2 minutes qO stability 22 to 3/10 seconds The formulation of the treatment liquid used in each treatment step is as follows. x2~3. r 0C (7) Water 700ml
Filling sand (I0 water salt) 20, 0g sodium sulfate (anhydrous) 100g sodium hydroxide /, add 0g water
/ , 001pH (J7 °C)
q, sr2/~310C water
trrOml Kodak Anti Calcium A
2.0ml sodium sulfite (anhydrous)
, og Eastman anti-fog shop? 0.22g Sodium Bromide (Anhydrous) 7.2oz Sodium Carbonate (Anhydrous) Co! , to g Sodium bicarbonate 2.7g Color developing agent: 4t-(N・ethyl・N-(β-methanesulfonamidoethyl)-m-toluidine, og water added /, θ01pH (27°C)
lo, ko■ stop
Water with prescription value 2/~310C
9 o o m17, oN sulfuric acid
Add 10ml water / ,0
01pH (,27°C) 0.9■
White Prescription value 32~4t3°C
water qooml potassium ferricyanide 410.0g sodium bromide (anhydrous)
Add kos, og water /
, 001 pHa 7°C≦, 0 20-310C water 700ml 1l Kodatsuk Anti-Calcium &'l 2 , Oml! ♂ Ammonium thiothiosulfate solution / ♂j ml sodium sulfite ÷ (anhydrous) to og bisulfite) IJium (anhydrous) ♂, add 4tg water to 7.001 pH (,! 7 °
C) , j■ stable
Prescription value/~27°C water/
, 0011 Kodatsu Stabilizer Adity"j O, lamll formali 7 (j 7.7% solution) /, JrOml Also, instead of step ① in the development process [A], use the following bleach accelerating bath to The development process [A ] Development processing CB) was carried out in the same manner as above.Furthermore, the sharpness of the red-sensitive layer was evaluated using the conventional MTF value.
900ml Sodium metabisulfite (anhydrous) io, og glacial acetic acid 2! , 0ml sodium acetate /θ, OgEDTA-aNa
o, 7gPBA-7j,
Add 6g water /, 0lpH (,
27°C) 3. r±0.2 (PBA-/is -
Represents monodimethylaminoethylisothioureacohydrochloride. ) 24t~3♂0C water 100ml gelatin o, sg sodium persulfate 33g sodium chloride
/j, 0g monosodium phosphate (anhydrous)
q,og phosphoric acid (rj%)
Add jml water
/,01pH(,27°C),2.7±O,
The results obtained are shown in Table 1. From the results in Table 2, it is clear that samples /j to /♂ according to the present invention show little decrease in A degree of cyan images even when subjected to bleaching treatment with weak oxidizing power, and have excellent sharpness. Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment filed on July 1, 1986 - Date

Claims (1)

[Scope of Claims] A halogenated compound characterized by containing at least one type of coupler represented by the following general formula (I) and at least one type of cyan coupler represented by the following general formulas (II) and (III). Silver color photographic material. General formula (I) A-PDI In the formula, A represents a group that reacts with the oxidized developing agent to cleave PDI, and after PDI is cleaved from A, it reacts with the oxidized developing agent to produce a development inhibitor. represents a group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aromatic group or a heterocyclic group, and R_
2 represents a group that can be substituted on the naphthol ring, R_3 represents an aliphatic group, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and Z_1 represents a hydrogen atom or a coupling-off group. Z_1 in general formula (II) and general formula (III) may be different from each other.
Z_2 represents -O-, -S-, or R_4-N-. However, R_4 represents a hydrogen atom or an organic substituent,
When a and b are plural, R_2 in general formula (II) and general formula (III) may be the same or different, and may be bonded to each other to form a ring. In general formula (III), R_2 and Z_2 or Z
_2 and Z_1 may be bonded to each other to form a ring. Also, R_1, R_2, R_3, R_4, Z_2
Alternatively, Z_1 may form a dimer or more multimer. Furthermore, Z_1 does not represent a development inhibitor or a group containing it.