JPS6385633A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent color reproducibility and capable of forming a magenta image having high sensitivity and high coloring density by incorporating a pyrazoloazole type magenta coupler and carboxylic acids having non-coloring and anti-diffusion properties in the same layer of the photosensitive material. CONSTITUTION:The titled material comprises the pyrazoloazole type magenta coupler shown by formula I and the carboxylic acids having the non-coloring and the anti-diffusion properties in the same layer of the photosensitive material. In formula I, R<1> and X are each hydrogen atom, etc., Za-Zc are each methine, a substituent, =N- or -NH- group, at least one of Za-Zb and Zb-Zc bindings is a double bond, and another of them is a single bond. When the Zb-Zc binding is the carbon-carbon double bond, said binding comprises the part of a aromatic ring. When R<1> or X forms a polymer of for example, more than a dimer, or Za, Zb or Zc is the substd. methine, a substd. methine comprises the polymer of for example, more than dimer. The concrete example of the compd. shown by formula I comprises preferably the compd. shown by formula I-1.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is a silver halide color photographic material that has excellent color reproducibility and formalin resistance, is highly sensitive, and has a high resistance to aging before development. This invention relates to a silver halide color photographic material with excellent stability.

(Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic 7th class amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that similar pigments can be produced and color images can be formed.

Among these, pyrazolone, cyanoacetophenone, indazolone, pyrazolobenzimidazole, and pyrazolotriazole couplers are used to form the magenta color image.

Hitherto, most of the pyrazolones have been widely used and researched as magenta image-forming couplers. ! - Pyrazolone couplers have excellent speed and efficiency in forming dyes, and the formed azomethine dyes have excellent fastness to light and heat, but they have absorption of yellow components around 4 J Onm, which is undesirable as magenta dyes. It was known that this caused the color to become cloudy.

As a magenta image forming bone nucleus that reduces this yellow component, British Patent No. 1. Pyrazolobenzimidazole bone core as described in U.S. Patent No. 0'17,612, U.S. Pat.
Pyrazolotrizole bone core described in No. 26.047, JP-A-Sho! Tar/62! The pyrazoloimidazole bone core described in No. 2, the pyrazolo pyrazole bone core described in No. 0-4 j 4 r, the same! Tar/7/ri! Pyrazolotriazole bone core described in No. 40-33! The pyrazolotetrazole bone core described in No. J2 is known.

The pigments formed by these are certainly all up to now in terms of absorbing unnecessary yellow components! -Pyrazolo/s. However, these couplers lack the speed and efficiency of forming dyes that are conventional! - Inferior to pyrazolones,
As a result, there were drawbacks such as low color density and sensitivity, and staining in undeveloped areas.

In addition, these couplers adsorb to the silver halide emulsion contained in the light-sensitive material during the production and/or storage of the light-sensitive material, gradually changing the performance of the emulsion. The activity of the coupler itself changes due to interaction with the contained Ag ions, and the P of the system changes.
It has become clear that changing the Ag content causes problems such as deterioration of the emulsion.

On the other hand, Japanese Patent Publication Sho<tt-4to4t, No. 22 claims that an alkyl-substituted phenoxyalkylcarboxylic acid is used as a solvent component of a coupler having an alkyl-substituted phenoxyalkanamide group. However, this patent not only does not include any description of the pyrazoloazole magenta coupler of the present invention, but also requires that both the coupler and the carboxylic acid have an alkyl-substituted phenoxyalkyl group, which is clearly different from the present invention. are different from each other.

Differences from these conventional techniques will be shown in examples.

(Objectives of the Invention) The first object of the present invention is to provide a silver halide color photographic material having a magenta image with excellent color reproducibility, high sensitivity, and high color density. An object of the present invention is to provide a silver halide color photographic material that exhibits little change in photographic performance during manufacturing and/or storage.
The third object is to provide a silver halide color photographic material that does not produce unnecessary capri or stain in unexposed areas during and after processing.

(Structure of the Invention) These objects of the present invention are characterized in that a pyrazoloazole magenta coupler represented by the following general formula [I] and a non-color-forming and diffusion-resistant carboxylic acid are contained in the same layer. This is achieved by silver halide color photographic light-sensitive materials.

General Formula (1) In the above formula, R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. Zb-Zc is carbon-
The case of a carbon double bond includes the case where it is part of an aromatic ring. When R or X forms a multimer of No. 2 or more, and when Za, Zb or Zc is a substituted methine, it also includes a case where a multimer of No. 22 or more is formed with the substituted methine.

The compounds used in the present invention will be explained in more detail below.

In the general formula (I), the term "multimer" means one having two or more groups represented by the general formula (I) in the molecule, and includes bis-forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by general formula (1) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine A copolymer may be prepared with a non-color-forming ethylene-like monomer that does not couple with the oxidized developer.

Among the pyrazoloazole magenta couplers represented by the general formula (1), preferred ones are those represented by the following general formula (II).
, (III), (IV), (V), (M), (■) and (■).

(n) (II[)(F/)
(V) (■) (■) (■) Among couplers represented by general formulas (I[) to (■), preferred for the purpose of the present invention are those represented by general formulas (n), (V) and (M). More preferred are those represented by the general formula (■).

In general formulas (II) to (■), R11, R12 and R may be the same or different, and each may be a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, or an aryloxy group. group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, hetero Represents a ring thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group,
X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom or sulfur atom and is decoupled. R11, R12, R13t or X may form a cibis form which is a covalent group.

It may also be in the form of a polymer coupler in which the coupler residues represented by general formulas (II) to (■) are present in the main chain or side chain of the polymer, and in particular derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred, in which case R11, R12, R13 or X represent a vinyl group or a linking group.

More specifically, R11, R12 and R13 are each a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an alkyl group (e.g. methyl group, propyl group, t-
Butyl group, trifluoromethyl group, tridecyl group, 3-
(2,y-di-t-amylphenoxy)propyl group,
Allyl group, codedecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclo butyl group, benzyl group, etc.), aryl group (e.g. phenyl group, <t-t--y 'Tylphenyl group 1.
2.4t-di-t-7mylphenyl group, gutetradecanamidophenyl group, etc.), heterocyclic group (e.g., cofuryl group, cochenyl group, 2-hyrimicinyl group, cobenzothiazolyl group, etc.), cyano group , alkoxy group (
For example, methquine group, ethoxy group, comethoxyethoxy group, λ-dodecyloxyethoxy group, comethanesulfonylethoxy group, etc.), aryloxy group (e.g.
phenoxy group, comethylphenoxy group, g-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g. copenzimidazolyloxy group, etc.), acyloxy group (e.g. acetoxy group, hexadecanoyloxy group) ,
etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy groups (e.g., trimethylsilyloxy group, etc.), sulfonyloxy groups (e.g., dodecylsulfonyloxy group) , etc.), acylamino groups (e.g.
Acetamide group, benzamide group, nato-2-decaneamide group, α-(2,q-di-t-amylphenoquine)butyramide)”L r -(j-t-butyluda-hydroxyphenoxy)butyramide group, α-(<= -(4t-
hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g., phenylamino group, cochloroanilino group, cochloroanilino!-tetradecanamideanilino group, cochlorho!-dodecyloxycarbonylanilino group, N-acetylanilino group, lino group, cochloro=!-(α-(3-t-butyl-y-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group, N,N-dibutylureido group) groups, etc.), imido groups (e.g., N-succinimide groups, 3-benzylhydantoynyl groups, a-(X-ethylhexanoylamino)phthalimide groups, etc.), sulfamoylamino groups (e.g., N
, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, λ-phenoxyethylthio group, 3-phenoxy Propylthio L 3-(a-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, =-butoxy-1-1-octylphenylthio group, 3- is ntadecylphenylthio group, carboxyphenylthio group, goutetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g. copenzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g. methoxycarbonylamino group, tetradecyloxycarbonyl group) amino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2.4t-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecane sulfone), amide group, benzenesulfonamide group, p-1 luenesulfonamide group, octadecanesulfonamide group, comethyloxy-rt-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl, S, N , N-cyphthylcarbamoyl group,
N-(codedecyloxyethyl)carbamoyl group, N
-Methyl-N-dodecylcarbamoyl group, N-(j-(
(2,41-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl groups (e.g., acetyl group, (,2,4t-di-tert-amylphenoxy))
acetyl group, benzoyl group, etc.), sulfamoyl group (
For example, N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(s-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, Famoyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octanesulfonyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.) ), alkoxycarbonyl group (e.g. Eva, methoxycarbonyl group, butyloxycarbonyl group,
(dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, 3-interdecyloxycarbonyl group, etc.), and X represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxy group, or a group connected by an oxygen atom (e.g. an acetoxy group, a propanoyloxy group, a benzoyloxy group,
-2+ ”-dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, g-cyanophenoxyl group, gumethanesulfonamidophenoxy L <t-methanesulfonylphenoxy group, α-naphthoxy group, J-A
! ! ntadecylkenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethoxy group, benzyloxy group, cophenethyloxy group, cophenoxyethoxy group,! -phenyltetrazolyloxy group, cobenzothiazolyloxy group, etc.), groups linked by nitrogen atoms (e.g. benzenesulfonamide group, N-ethyltoluenesulfonamide group, butafluorobutanamide group 1.2 .J, 4t, j, t-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group N.

N-diethylsulfamoylamino group, /-pi is lysyl Lt, t-dimethyl-co, cudioquine-3-oxazolidinyl group, /-benzyl-ethoxy-3-hydantoynyl group, 2N-7, /-dioxo-, ? (2H)-oxo-7,2-benzointhiazolyl group, -oxo7
．． 2-dihydro/-pyridinyl group, imidazolyl group,
pyrazolyl group, 3. ! -diethyl-7,2,4t-)riazol-/-yl,j '1fcltit jromobenzotriazol-/-yl,! -methyl=7,
2゜j, Q) Riazol-/-yl group, penzimitazoryl group, 3-benzyl-/-hydantoinyl group, /-benzyl-! -hexadecyloxy-3-hydantoynyl group,! -methyl/-tetrazolyl group, etc.), arylazo group (e.g., goomethoxyphenylazo group, Hiro-pivaloylaminophenylazo group, corner 7-tylazo group,
3-methyl-g-hydroxyphenylazo group, etc.), groups linked by a sulfur atom (e.g., phenylthio group, λ-
Carboxyphenylthio group, comethoxy! -t-octylphenylthio group, goomethanesulfonylphenylthio group, teroctanesulfonamidophenylthio group,
Coptoxyphenyltheo group, 2-(2-hegisansulfonylethyl)-! -tert-octylphenylthio group, benzylthio group, λ-cyanoethylthio group, /-ethoxycarbonyl) IJ decylthio group,! -phenyl-2°3.4t, -tetrazolylthio group, 2-benzothiazolylthio group, -1dodecylthio- and -1thiophenylthio group, cophenyl-3-)"y'sil-/.

J, (7-) riazolyl-! -thio group, etc.).

In couplers of general formulas CI [] and [■], R
12 and R13 combine! A negative or two-membered ring may be formed.

When R11, R12, RL3 or X becomes a divalent group to form a bis body, preferably R, R.

R13 is a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, /, 10-decylene group, -CH
2CH2-O-CH2CH2-1 etc.), a substituted or unsubstituted phenylene group (e.g. /, 4t-) unicine group,
/, 3-phenylene group, -NHCO-R14-CONH- group (R14 represents a substituted or unsubstituted alkylene group or phenylene group,
For example, -NHCOCH2CH2CONH-2H3 -NHCOCH2C-CH2CONH-H3 group (R14 represents a substituted or unsubstituted alkylene group in Table H3, a heptavalent group converted into a divalent group at an appropriate position).

General formula (■), (I[I), (IV), (V), (M)
, (■) and (■) are included in the vinyl monomer, the linking group represented by R11, R12, R13 or X is an alkylene group (substituted or unsubstituted alkylene group, For example, methylene group, ethylene t
s, /, 10--7' silene group, -CH2CH20CH
2CH2-2, etc.), phenylene group (substituted or unsubstituted 7-enylene group, such as /, 4t-phenylene group, /
, 3-phenylene group, -NHCO-1-CONH-1-
0-5-OCO- and aralkylene groups (for example, groups formed in combination with Lε).

Preferred linking groups include the following.

-NHCO-2-CH2CH2-1 〇-CH2CH20-CH2CH2-NHCO-1 The vinyl group has the general formula (I[), (Ill), (IV), (V
), (M), (■)! Alternatively, substituents other than those represented by (■) may be used, and preferred substituents are hydrogen atoms,
Represents a chlorine atom or a lower alkyl group having 7 to 9 carbon atoms (eg, methyl group, ethyl group).

General formula (II), (II[), (IV), (V), (M
), (■) and (■) are copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers. Good too.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate), 1so-butyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene) , vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (
Examples include vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-copyrrolidone, N-vinylpyridine, and Co- and Hina-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical properties of the copolymer formed and the /'-strapping chemistry. The photographic colloidal composition can be selected such that its properties such as solubility, compatibility with binders such as gelatin of the photographic colloidal composition, its flexibility, thermal stability, etc., are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

The non-color-forming and diffusion-resistant carboxylic acids used in the present invention are represented by the following general formula (IX).

General formula (■) (R14-COO-)nMn+ R14 represents a substituent that provides diffusion resistance to the compound of general formula (IX), Mn+ represents a hydrogen ion, metal ion or ammonium ion, and n is / Represents an integer between .

The group represented by R14 that imparts diffusion resistance to the compound of general formula (■) has a total carbon number of ♂ to <10, preferably /co to 32, and has a straight or branched alkyl group (for example, a methyl group, Ethyl group, n-propyl group, n-butyl group, 1
so-butyl group, n- is butyl group, n-heptyl group, n
-nonyl L n-undecyl group, n-)lysosyl group, etc.)
, alkenyl groups (e.g. allyl group, decenyl group, dodecenyl group, oleyl group, etc.), cycloalkyl groups (e.g. cyclopropyl group, cyclo means butyl group, cyclohexyl group, norbornyl group, etc.), alkynyl groups (e.g. propargyl group, etc.), Aralkyl groups (e.g. benzyl group, phenethyl group, etc.), cycloalkyl groups (side-light cyclopentenyl group, cyclohexenyl group, etc.), aryl groups (e.g. phenyl group, α-naphthyl group, β-naphthyl group, etc.)
or a heterocyclic group (i.e. a nitrogen atom as a heteroatom,
At least 7 atoms of oxygen or sulfur atoms are constituent elements of the ring! to 2-membered monocyclic or condensed ring heterocyclic group, such as copyridyl group, goupyridyl group, coquinolyl group, 2-furyl group, cochenyl group, goopyrazolyl group, terimidazolyl group, etc.), which have a total number of carbon atoms of is in the range of male to aO, and the number of substituents may be 7 or more. (However, among these groups, those having 2 or more carbon atoms may be unsubstituted.) Examples of substituents for these groups include halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms,
iodine atom, etc.), nitro group, cyano group, hydroxy group,
Carboxy group, sulfo group, mercapto group, alkoxy group (e.g. methoxy group, ethoxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group, =, tert-pentylphenoxy group, J-tert-
Butyl-g-hydroxyphenoxy group, 3-tadecylphenoxy group, λ-chloro 4t-tert
--<butylphenoxy group, =-cyanophenoxy group, -tert-octylphenoxy group, q-dodecyloxyphenoxy group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, dodecylthio group, etc.), arylthio group (e.g. phenylthio group) group, q-dodecyl phenylthio group, q-octyloxyphenylthio group, etc.),
Alkylsulfonyl group (methylsulfonyl group, benzylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl Lp-t')
rusulfonyl group, kudodecylphenylsulfonyl fi
, Q-doa' siloxyphenylsulfonyl group, etc.), carbonamide group (e.g., acetamide group, benzamide group, N-phenylacetamide group, tetradecaneamide group, etc.), sulfonamide group (e.g., methylsulfonamide group, phenyl sulfonamide group, p-tolylsulfonamide group, hexadecylsulfonamide group, etc.), amino group (e.g. amine group, dimethylamino group, pyrrolidyl group, pyrallyl group, dodecylamino group, anilino group, etc.),
Carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, N-dodecylcarbamoyl group, etc.)
, alkoxycarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl LP-te)
rt-butylphenoxycarbonyl group, etc.), acyloxy group (e.g., acetoxy group, etc.), sulfamoyl group NF
IJ, thasulfamoyl group, dimethylsulfamoyl group, dimethylsulfamoyl group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), imide group (e.g. succinimide group, etc.), ureido group (e.g. 3.3 -dimethylureido group, etc.), alkoxycarbonylamino group (e.g., ethoxycarbonylamino group, etc.), aryl group (e.g., phenyl group, P-t+) group, p-methoxyphenyl group, α-su7tyl group, β -naphthyl group, etc.) and heterocyclic groups (e.g. /-imidazolyl group, /-pyrazolyl group,
Copyridyl group, goupyridyl group, coky/')yl group,
(cofuryl group, cochenyl group, /-benzotriazolyl group, phthalimide group, etc.).

When R14 is an aryl group, a heterocyclic group, or an aralkyl group, substituents for these groups include, in addition to the above-mentioned substituents, an alkyl group (e.g., methyl group, ethyl group, 1so-propyl group, tert-butyl group, tert-butyl group, tert-butyl group, tert-butyl group, -pentyl group, t
ert-hexyl group, /, /, j,! -tetramethylbutyl group, etc.), alkenyl groups (e.g. allyl group, hexenyl group, oleyl group, etc.), alkynyl groups (e.g. propargyl group, etc.), and cycloalkyl groups (e.g. cyclopropyl group, cyclo means butyl group, cyclohexyl group, etc.) can be cited as an example.

Mn+ is an ion of group 1 of the periodic table (e.g. H, Na
, K, Cs, etc.), group II ions (e.g. M g 2+, Ca2+, Ba2+, etc.), group 1 ions (e.g. Fe2+, Fe3+, Co2+, C
O3+, Ni2+, etc.), and 77monium ions (represented as R16-N-R18), but preferably ions of group 1 of the periodic table, group
group ions, and ammonium ions. Particularly preferred are H+, N a +, K+, and NH4+, and most preferred is H+.

Here, R15, R16\R17, and R18 are hydrogen atoms, alkyl groups (e.g., methyl group, ethyl group, 1-butyl group, etc.), substituted alkyl groups, aralkyl groups (e.g., benzyl group, phenethyl group, etc.), substituted aralkyl groups, Represents an aryl group (for example, a phenyl group, a naphthyl group, etc.) and a substituted aryl group, the number of carbon atoms from R15 to R18 does not exceed coθ, and a ring may be formed between R15 and R18, Also, they may be the same or different.

Examples of substituents for alkyl groups, aralkyl groups, and aryl groups include nitro groups, hydroxyl groups, cyan groups, sulfo groups, alkoxy groups (e.g., methoxy groups), aryloxy groups (e.g., phenoxy groups), and acyloxy groups (e.g., acetoxy groups). ), carbonamide groups (e.g. acetamide groups), sulfonamide groups (e.g. methylsulfonamide groups), sulfamoyl groups (e.g. methylsulfamoyl groups), halogen atoms (e.g. fluorine, chlorine,
(bromine), carboxy group, carbamoyl group (for example, methylcarbamoyl group), alkoxycarbonyl group (for example, methoxycarbonyl group), and sulfonyl group (for example, methylsulfonyl group). When there are two or more of these substituents, they may be the same or different.

Next, preferred specific examples of the compounds represented by the general formula (I) will be shown, but the invention is not limited thereto.

(■-ko) (1-j) <1-4t) H3 し M3 (1-j) (l-/g) ([-/1) (1-7a) H3 (1-/?) (!- 20) (r-here) (■-=3) (I-24t) (1-jJ) (1-,?I CH3 shin3 (I-jj) (CH2)3 (!-3) (■- 39) (!-gO) H3 <1-4t/) (1-qco) (1-4tj) The coupler represented by the general formula (I) of the present invention can be prepared by the method described in the following documents, etc. It can be synthesized according to the same method.

Compounds of general formula (II) and (1'l/) are disclosed in JP-A-Sho!
? -/62!41♂ etc., compounds of the general formula ([[ / etc., the compound of general formula (M) is disclosed in JP-A-Sho! Tar/7/ri! O and J? -277
4t! etc., the compound of general formula (■) is disclosed in JP-A-60-3
3! ! Also, the compound of general formula (■) is patented in the United States! , OA/, 4t32, etc., respectively.

Also, Tokukai Akira! ? -9=04t! No., Tokukai Akira! Day/7
7. No. 633, Tokukai Shojter/2g, No. 34, Tokukai Sho! Tar/No. 77.169, Tokukai Sho! -1777, J
'! No. 7, Tokukai Akira! Tar/77! ! No. 4, Tokukai Akira! The highly color-forming ballast group described in Patent No. 77.3jj etc. is applicable to any of the compounds of the above general formulas (n) to (■).

Preferred specific examples of the compounds represented by the general formula (■) will be shown below, but the invention is not limited thereto.

(A-/) (A-2) (t) (-'5) 111 (A-3) (A-4t) C17H35COONH4 (A-t) (to A-) α (A-7) (A-♂ ) C□5H3□C00H (A-ta) (A-10) (A-//) (A-/1) (A-/4t) H35Ci8-CH-C0OH CH2-C00H (A-/j) (n )H25C12-CH-C0OH CH2-C00H (A-/6) Di(A-/7) (A-/♂) C4H9(t) Shi121125 (A-/ri) (A-20) (A-co/ ) (A-, 22) (A-, 2j) Shihachi (A-, 2μ) (A-Kori (A-26) (A-27) (tλ and 5M11 (A-Kori (A-λR) ) (A-30) (A-3/) (A-32) (A-jj) (A-3) (A-3j) The magenta coupler of the present invention is added to the same layer as the carboxylic acid of the present invention. However, the amount of magenta coupler added is 0.07~/, θg/m2, preferably o, ot~0
．． 6g/m2, more preferably 0. /~0. jg/m2
It is.

The weight ratio of the carboxylic acids of the present invention to the magenta coupler of the present invention contained in the same layer is 0.07 to 10θ times, preferably 0.0! ~20 times, more preferably 0.7
~! It's double.

The magenta coupler of the present invention and the carboxylic acids of the present invention may be used in any layer in the light-sensitive material as long as they are used in the same layer, but they are preferably in the red-sensitive silver halide emulsion layer or its adjacent layer, and more preferably in the red-sensitive silver halide emulsion layer or its adjacent layer. This is a photosensitive emulsion layer.

The magenta coupler of the present invention can be dispersed and mixed with the carboxylic acids of the present invention alone or in combination of two or more thereof, and can also be used in combination with a conventionally known high-boiling organic solvent as described below.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mole or less silver iodide. Particularly preferred is about 2 to 2! It is silver iodobromide containing silver iodide up to molti.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may have crystal defects such as, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.7 microns or less, or large grains with a projected area diameter of up to about 70 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Flat 77 Go 4t3
(/ri2/February), pp. 22-23, '1. Emulsion preparation and
types)” and the same, A/lr2/l (/ri7
(year//month), 64t/page, "Physics and Chemistry of Photography" by Glafkide, published by Paul Montell (P, Glafkide)
s, Chimie etPhysique Pho
tographique Paul Montel,
/ 9 A 7), "Photographic Emulsion Chemistry" by Duffin,
Published by Focal Press (G, F, Duff in.

Photographic Emulsion Che
mistry(Focal Press, /rigg
6), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L. Zelikman et al.
Al、Makingand Coating Pho
tographic emulsion.

Focal Press, / 9 A'! ), etc.).

U.S. Patent No. j, 77<t, 322, 3.6! !
Also preferred are the monodisperse emulsions described in British Patent Nos. 1,4e/j, 7q/ and the like.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.

Photographic 5science an
dEngineering), Volume 74, 241
1 A-2t7 pages (/70 years); U.S. Patent No.
<t3<l, , issue 22, same & , &/4t, 31
No. 0, same Q, 4t33, 04t/No., same gu, gu 3
No. 120 and British Patent No. 2. It can be easily prepared by the method described in, for example, No. //2,167.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Ji
/ 7 d 413 and i% / / 7 / 6, 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 search disclosures, and the locations listed are shown in the table below.

Additives RD/7t4t3 RD/r7/l/
Chemical sensitizers, page 23, page 64t♂ right column ko Sensitivity increasing agent Same as above Brightening agent koq page 7 anti-stinting agent page 25 right column Bu! Page 0 left to right column!
Dye image stabilizer page 2j hardener page koi/page left column 10
Binder, page 2 Same as above // Plasticizer, lubricant, page 27 6! θRight Column Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in Research Disclosure (RD) Ya/7 Otsugu 3, ■-C to G. has been done.

As a yellow coupler, for example, U.S. Patent No. 3. 3. ! , jO1 No., No. 6.20, No. 32/, No. 0.2q, No. 4t0/, No. 7j, Tokko Sho! ♂-10739, British Patent No. 7,4t26
．． No. 0, No. 1. &74.7gθ and the like are preferred.

As a magenta coupler, use other than the pyrazoloazole coupler of the present invention! -Pyrazolone compounds are preferred, and US Pat.
Particularly preferred are those described in European Patent No. 73.53.

Cyan couplers include phenolic and naphthol couplers, as described in US Pat.

No. 032.272, No. 9. /Da4. J? No. 4, same No. 2, 2 pieces! , No. 233, No. 4t, 2≦, 2θθ No., No. 3 & 9. No. 2.10/171, No. 2,77.2. /I λ No. 2. /ri J-,
e! No. 2, No. J, No. 772, No. 00j, No. 3 of the same
．． No. 7j1.301, No. 33, No. 0//, No. K, No. j27.773, West German Patent Publication No. 3.32,
7 Kota, European Patent No. 1u/, j4J-A, US Patent No. j, 4t&≦, 6 Kota, European Patent No. 1u/, j4J-A, US Patent No. ,
? Tata, same number, 4t! Preferably, those described in European Patent No. 1, TTQ, Patent No. Q, Da 27,767, European Patent No. 1t/, A2tk, etc. are preferred.

Colored couplers that correct unnecessary absorption of color-forming dyes are disclosed in Research Disclosure /7t'13, ■-G, U.S. Patent No. G, /A3, No. 470, Special Publication! 7-3ri 4t/3, U.S. Patent No. q.

004t, No. 92, No. &, /31.2jr, British Patent No. 1. /'At...! Those described in No. g1 are preferred.

Couplers whose coloring dyes have appropriate diffusivity are disclosed in U.S. Pat. /Ko! ,! No. 70, European Patent No. 96,170, West German Patent (
The one described in Publication) No. 3.2!4t, No. 633 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 2//, No. 347.122, British Patent No. 2/θ2, No. 73, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned RD/7. <G3,
Patents described in sections ■~F, JP-A No. 7-/J-/9'
14t, same j7-/14t co3g, same otsu 0-/rK24
Preferably, those described in U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 7, θri 7, /4
tO issue, same issue, /J/, // issue, Tokukaisho! Day/
! 76jr, same! Those described in 770♂g θ are preferred.

In addition, as a coupler that can be used in the photosensitive material of the present invention, US Patent No. '1. /30,4t-7 etc., U.S. Patent No. 4t, 2/3.4t72
No. 331.393, No. 11. Jlo, 6
The multi-equivalent coupler described in No. 77 etc., JP-A-60-/r!
the law of nature! Examples include DIR redox compound-releasing couplers described in .theta., etc.; European Patent No. 773.30.2), and couplers that release dyes that exhibit aftercoloring after separation as described in European Patent No. 773.30.2).

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. 9. /9ri.

JtJ No., West German Patent Application (OLS) No. 1/.

No. 274 and No. 2 of the same. Yori/, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7t'lj, page 22, and Tomb/77/l, page 4t7, right column to page 69♂, left column.

The color photographic material according to the present invention has the above-mentioned RD, Mu/76 Da 3, 2/2 to 2 pages, and the same, AI/7/l ≦
! / It can be developed by the usual methods described in the left column to right column.

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 countercurrent washing in tanks larger than one to conserve water. For stabilization treatment, use Tokukaisho instead of the water washing process! 7-♂! A typical example is a multistage countercurrent stabilization treatment as described in No. 3 of the present invention.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color positive film, and color reversal paper. The present invention can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in Research Disclosure/7/, 23 (February 2013).

〔Example〕

The present invention will be described in detail below with reference to Examples, but the embodiments of the present invention are not limited to the following.

Example-/ On a subbed cellulose triacetate film support,
A multilayer color photosensitive material 10/ was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in units of g/m2, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes and couplers, the coating amounts are expressed in moles per mole of silver halide in the same layer.

(Sample 10/) 7th layer: Antihalation layer black colloidal silver...Silver 0. /? Gelatin -... /, 'IO second layer; middle layer,! -Gt- is tadecylhydroquinone...0.7/C-7
・ ・ ・ 0.07 C-J ・ ・ ・ 0.02
U-/ ・ ・ ・ ・ o,
orU-2・ ・ ・ ・ 0.0♂ HBS-/ ・ ・ ・ ・ 0.10
HBS -, 2----o, oa Gelatin... /, 04 as third layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion (3 mol of silver iodide, average grain size 0.♂μ) ...Silver 0. ! 0 sensitizing dye■
...6. ri×10-5 sensitizing dye■
...y, r x 1o-5 sensitizing dye■ ...
J, /X70-4 sensitizing dye■ ...<t, o
xlo-sC-tsu...0. / Rini) (B S -/ ・・・o, oo
tC-10...0.00!0 Gelatin...7.20 9th layer;
7th green-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide! Morti, average grain size 0./lμ) ・・・Silver/, /j sensitizing dye■
...j, /×10-5 sensitizing dye I[-
---y, txto-5 sensitizing dye ■...ko, 3 x 10-4 sensitizing dye ■...3.0x/
θ-5C-2...θ, 010 C-3...o, ootr C-10...... θ, 0041HBS-
/ ...θ, Q0! gelatin
・・・／、! 00 No. 5; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide/θ mole, average grain size/,!μ)...Silver/,! O sensitizing dye■
...! , 4tX10-5 sensitizing dye■
.../, 4t x 10-5 sensitizing dye ■...
... 4t x 10-4 sensitizing dye■ ...3
．． /×1O-6C-r...θ
, 0/, 2C-3・・・・・o,oo3C
−q ・ ・ ・ ・
0.32HBS-/ ・ ・
・ ・ 0.32 gelatin ・ ・
・ 7.63 6th layer; Intermediate layer gelatin Φ... /, O66 7th;
7th green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide emulsion, average grain size 0./μ)...Silver 0.3! Sensitizing dye V
...3.0×10-5 sensitizing dye■
.../, Ox10-4 sensitizing dye■ ...
j, I×/θ-4C-4・ ・ ・ ・ 0.23θ C-/ ・ ・ ・ ・
0.010C-7...0.0<1C-/...θ, 0! H3B
−/ ・・・ θ, coθ gelatin
...0.70th ♂ layer; th green-sensitive emulsion layer silver iodobromide emulsion (silver iodide! malt, average grain size 0.♂jμ) ...silver/, 2! Sensitizing dye■
...Co, /x70-5 sensitizing dye■
...7.0X/θ-5 sensitizing dye■ ...
λ, I×7O-4C-t
・ ・ ・ ・ θ , θ3IC-♂
・ ・ ・ ・ o, ooeC-/
・ ・ ・ ・ θ
, 0QkoC-7・ ・ ・ θ , 0/! H3B-/ ・ ・ ・ ・
0,/! Gelatin... o,
r.

2nd layer; 3rd green-sensitive emulsion layer Silver iodobromide (silver iodide/θ mole, average grain size/, !μ) .....Kushi λ, 20 sensitizing dye■
...J, j×/θ-5 sensitizing dye■
・・・・♂, Q×/θ-5 sensitizing dye■ ・・
・・3.0×/θ−4C−// ・・・
・θ, 0/2C-/・・・Q,
θ0/HBS-2... 0.6 Digelatin 1Ijl 7.24 as 70th
Layer: Yellow filter layer Yellow colloidal silver...Silver 0. θ! Ko,! −
G-t- is tadecylhydroquinone...Q, θ3 gelatin...0. the law of nature! 1st/Layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 molt, average grain size 0.6μ) ... Silver θ, Co sensitizing dye■
...J, J-X10-4C-9...
0. Core C-/...o, oojH
BS-/...ol, 2♂ gelatin.../, ko? 12th layer: Blue-sensitive emulsion layer silver iodobromide emulsion (iodide fli10 mol, molar grain size/, θ
μ) ...Silver o, t, tz sensitizing dye■ ・
... Ko, /×/θ-4C-2...0.0ji? HBS-/... θ, θ3 gelatin... θ, g6 73rd layer; 3rd
Blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 70 moles, average grain size/, ♂μ) ...Silver 0.77 sensitizing dye■
....., 2X10-'C-ta
...0,03tHBS-/
... O0θ7 gelatin
...0.69 74th layer: 1st capture layer silver iodobromide (1 mol of silver iodide, average grain size 0.07μ) ... Silver θ,! U-i
...0. //U-co
...0. /7p-Butyl hydroxybenzoate...0.0/2HBS-/...
・ O, DeQ 1st layer: 1st protective layer polymethyl methacrylate particles (diameter approx./,! μm)...0. jri S-7...
・・ 0. /! S-, 2... Q, 10 Gelatin... 0.72 In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each layer.

(Sample/θco~10j) The compound of the present invention (A
-2) (A-t) (A-/ko) and (A-/j)
were added to each layer at θ and 10 g/m2, and samples 702~
10! It was created.

(Sample 70≦~//) Coupler C-g in the 7th layer and 1st layer of Sample 10/ is 0.7
Sample 10/~10 in the same manner except that the mole times were replaced.
Sample 706~//! with the same pressure as j! It was created.

These samples were subjected to imagewise exposure with white light, and then subjected to Process A below υ using an automatic processor.

Processing A Color development 3 minutes/! Bleach for 7 minutes Bleach fix for 3 minutes/! Second washing■ <to seconds washing■ 7 minutes stable 4tO seconds drying (!0°C) /min/! Sec. In the above treatment steps, water washing (1) and (2) were performed using a countercurrent water washing method from (1) to (2). Next, the composition of each treatment liquid will be described.

The amount of replenishment of the processing solution in the can was 20 θ ml for color development per m 2 of color photosensitive material, and ♂ θ 0 ml for all other matters including water washing. Also, the amount of pre-bath carried into the water washing process is color photosensitive material/m2.
Hit! It was Oml.

Color development retention solution> Mother solution Replenisher diethylenetriaminepentaacetic acid /, Og /, /g/-hydroxylthylidene-/, /- Diphosphonic acid Co, Og 2.2g Sodium sulfite <t, og 9.9g Potassium carbonate 30 .0g 3 pieces, og potassium bromide
/, '1g 0.7g potassium iodide /
, 3 mg -hydroxylamine sulfate co, g, 2. Buga-(N
-ethyl-N-β-hydroxyethylamino) -comethylaniline sulfate g, tg t, og Add water /, Ol /, 01 pH 10, θ
10.0! Bleaching solution> Mother liquor/replenisher Common ethylenediaminetetraacetic acid ferric ammonium salt /20, Og ethylenediaminetetraacetic acid dibasic ammonium salt 70.0g Ammonium nitrate 10.0g Ammonium bromide 100.0g Bleach accelerator
! × Add 70-3 mol ammonia water p
Ht, s Add water /, Ol
Bleach-fix solution> Ethylenediaminetetraacetic acid ferric ammonium salt common to mother solution and replenisher! 0. θg Ethylenediaminetetraacetic acid disodium salt 1.0g sodium sulfite / 2.0g ammonium thiosulfate aqueous solution (70%) x < toml Add ammonia water pH 7.3 Add water
/l washing water> Tap water containing calcium ion j-2mg/l smagnesium ion 7, Jmg// was filled with an H-swollen acidic cation exchange resin and an OH-type swollen basic anion-exchange resin and passed through nine columns. water, calcium ion/, 2mg
20 mg of sodium incyanurate dichloride was added to water treated with 0.11 mg/l of magnesium ion/l.

Stabilizing solution> Mother solution/replenisher common formalin (37% W/V) 2.0 ml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Ethylenediaminetetraacetic acid di-sodium salt 0. θ! g Add water / lpHr / dry > What is the drying temperature? The temperature was set to 0°C.

Similarly, the following treatment B was carried out using a new solution.

Processing B Color development 3 minutes/! seconds floating white minutes 30 seconds Wash with water for 70 seconds Fixed arrival time: q minutes, 20 seconds Wash with water for 3 minutes/! seconds Anonymous / minute θ! seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, Og/-hydroxyethylidene- /, /-diphosphonic acid co, og Sodium sulfite 9.0g Potassium carbonate
3theta,og potassium bromide
/, g potassium iodide
/ , J rng hydroxylamine sulfate
j, 4tg9-(N-ethyl-N-β-hydroxyethylamine) monomethylaniline sulfate, tg Add water /, θlpH/θ,
O Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt 100. Og ethylenediaminetetraacetic acid disodium salt 10, 0g ammonium bromide /! θ, og ammonium nitrate Add 10.0g water
/, 0lpHt,.

Fixer Ethylenediaminetetraacetic acid disodium salt /, 0 g Sodium sulfite 9.0 g Ammonium thiosulfate aqueous solution (2θ thi) /';#, Om1 Add g water to q, Om1 sodium bisulfite
/, 0 lpHJ, Otsu stabilized formalin (RI 0%), 2, 0 ml
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) o, 3g water was added /, θl These samples were t, t
Treatment B was carried out by contacting (a) θ ppm and (b) formaldehyde vapor of 10 ppm for 24 hours under conditions of a relative phase change of 70%, followed by imagewise exposure.

Exposure amount x Dm in CMS is expressed as Dm(a) and Dm(b) in Table 1 as Dm(b)/Dm(a)xlooo(h).

Also, the difference Dmin in the minimum magenta density between processing A and processing B
A Dmin B is also shown in Table 1.

From Table 1, samples of the present invention 107~/10, //ko~//
! is highly sensitive and has good formaldehyde gas resistance.
Moreover, it is clear that there is little magentastin (processing variation) due to processing.

EXAMPLE A multilayer color photographic material having each layer having the composition shown below was prepared in the same manner as in Example.

(Sample #07) 1st layer (antihalation layer) Black colloidal silver Oo, 2 gelatin /, 3C-/
... O1θ6UV-/
o, /UV-2o,2 HBS-/ ... 0. orHBS
-2... O0θ/ 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.02μ)... 0.7! gelatin
/, θC-3・ ・ ・
・θ, OHBS-/
0. /Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide λ molar ratio, average grain size 0.3μ) O, ggelatin
0.1 sensitizing dye I
.../ , 0x10-4 sensitizing dye ■ ...
・3.0×70-4 sensitizing dye ■・・・・／
×1O-5C-/2 ・・・o, ot
.

C-/3...0.07jC-/!
...0.0/θC-j
...0. θ3HBS-/
... θ, 03HBS-3...0. Q/
Q-th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! molar coefficient, average grain size θ, !μ) 0.7 Sensitizing dye I ... / × 10-4 increase Sensitizing dye■ ...3x/θ-4 sensitizing dye■
・・・・・・ /×7O-5C-/ko
・ ・ ・ ・ 0.24tC-73・ ・
・ ・ 0.24tC-10・ ・ ・ ・ 0
．． 0j C-,z---o,o
4tHBS-co ・ ・ ・ ・
o, orHBS-3--・ 0.70th! Layer (Third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mole coefficient average grain size 0.2μ) /,0 Gelatin /.0 Sensitizing dye 1 /×10-4 Sensitizing dye U
3×10-4 sensitizing dye m
/”xlo-5C-J
...0.0IC-da...
... θ, θIC-5θ, / C-/ko ... 0. o3HBS-
3... 0. θ3 HBS-ko ... 0.07th ≦ layer (
(middle layer) Gelatin 7.0(n)-
Sodium octadecylhydroquinone sulfonate...Q, 03HBS-/
... θ, or 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide q molar ratio, average grain size 0.3 μ) ... θ, 3θ sensitizing dye■
...! ×/θ-4 sensitizing dye■
... Ko×/θ-4 gelatin
/,0C-/da
0.2C-/・・・・・
0.0IC-7... θ, 0! HBS-/ o, r th male layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! molar ratio, average grain size o, rμ) o, t, sensitizing dye V... ! X10-4 sensitizing dye■
...=×70-4C-/ na
・ ・ ・ ・ 0.2IC-/
・ ・ ・ ・ θ , 0
/2C-7・・・・・0,θ32C−/・・・・・・
O, θ3HBS-/
o, 2nd layer (3rd green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide with mulch, average grain size 0.7μ)...O0♂! gelatin
7.0 Sensitizing dye V
...J,! X/θ-4 sensitizing dye■...
・/, g×1O-4C-/l ・・
... 0.10C-7... 0.0/C-/ ... θ, θHBS
-ko...0.10HBS-3...
-・0.0! 1st θ layer (yellow filter layer) Gelatin /1.2C-/
7... θ, 2θ,! -G-t
-Octylhydroquinone 0. /HBS-
/ o, s 1st/layer (first curved emulsion layer) Silver iodobromide emulsion (silver iodide qmolti, average grain size 0.3μ) 0.4t gelatin 7.0 Sensitizing dye■
... ko×/θ-4C-qo, riC-7! ...0.0! HBS-
Co θ, -72nd layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide/θ mole, average grain size/, !μ) 0. ! gelatin
0.1 sensitizing dye V
.../X/θ-4C-9
...0.2IC-/!・・・・・・
0.0! HBS-,? ... θ
, θ2 13th layer (7th protective layer) Gelatin O0! Ultraviolet absorber UV-10, / Same as above UV-x...0.2 HBS-/...0.0/HBS
-Co...0.07 Layer 74 (second protective layer) Gelatin...o, t, tt polymethyl methacrylate particles (diameter/,!μ)...0.2 Dura Agent H-
10,4t Formaldehyde scavenger 8-/θ,/Formaldehyde scavenger S-co θ,3 In addition to the above-mentioned components, gelatin hardener H-2 and a surfactant were added as coating aids to each layer.

(Sample-〇2~2Q&) o, /zg/m2 in the second layer of sample 20/ and 0. Ojg/m2 Compounds of the present invention (A-, <) (A-ta) and (A-, ?@) were added, and the samples were
3 and 20 were produced.

(Samples KO! ~ KO/Ni) Coupler C- in the 1st and 9th layers of samples 207-204t
/4t to C-/ Q, ♂! times molar, the coupler of the invention ((-x2)o, tt times molar and (1-!j) 0.6
Samples 07 to 20e were prepared in the same manner as samples 07 to 20e except that 0 was replaced with twice the mole amount. ~Co/6 was produced.

These samples were subjected to imagewise exposure to white light and green light and subjected to Process A in Example/. The photographic performance obtained is shown in Table 1. The degree of color staining in Table 2 indicates the yellow density obtained by subtracting the fog density at the exposure amount at which the magenta density of the strips obtained by exposure to green light is capri+7.0.

Also, after exposure, 4t0°C1 relative humidity? Treatment A was performed by leaving it for 7 days under conditions of θ% (forced deterioration conditions).

From Table 2, it can be seen that the samples of the present invention have high sensitivity, have little change in photographic performance under forced deterioration conditions, and have a low degree of color staining, which is favorable for color reproducibility.

Structure of the compound used in Example/C-/3 -/a α C-/O α and H2-doH2 HBS-/) licresyl phosphate HBS-, l
Diptyl phthalate HB S -J ToIJ -n-hexyl phosphate CH2=CH-8O2-CH2CONI(-CH2
CH2=CH-8O2-CH2-CONH-CH2H-
Sensitizing dye ■ ■ 2H5 2H5 ■ C2H5 Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment 1, case description Showa t/year patent application No. 2 J/j00
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant 4. Subject of the amendment Column 5, "Detailed explanation of the invention" of the specification, Contents of the amendment The description in the “Detailed Description of the Invention” section of
to correct.

/) Page 10, line 76 "Allyl group" delete.

j) Page io, rows 1 to 1 "Cyclo is an inter group" "Cyclo is an ethyl group" and correct it.

3) 7th≠page 73rd line “UV-/j “U-/J and correct it.

≠) Page 7≠ / Hiroyukime "UV-2" "U-co" and correct it.

page 10, line 1 “UV-/j rtJ-/J and correct it.

6) Page 10, line 7 "Uv-2" "U-2" and correct it.

Claims (1)

[Scope of Claims] A silver halide color photograph characterized by containing a pyrazoloazole magenta coupler represented by the following general formula [I] and a non-color-forming and diffusion-resistant carboxylic acid in the same layer. photosensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R^1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group that can be separated by Za, Zb
and Zc is methine, substituted methine, =N- or -NH
- represents a Za-Zb bond and a Zb-Zc bond, one of which is a double bond and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. When R^1 or X forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. .