JPH0223338A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the durability of a magenta colored picture against light and moist and hot environments by incorporating a specified compd. in the title material contg. an another specified pyrazoloazole type coupler. CONSTITUTION:At least one kind of the pyrazoloazole type coupler shown by formula I and at least one kind of the compd. shown by formula II are incorporated in the photosensitive material respectively. In formula I, R1 is hydrogen atom or a substituting group, X is hydrogen atom or a group capable of being released by a coupling reaction with the oxidant of an aromatic primary amine developing agent, Z is a nonmetal atomic group necessary for forming a nitrogen contg. heterocyclic ring. In formula II, R21 is hydrogen or halogen atom, alkyl, alkoxy, alkylthio, cyano, a heterocyclic ring, hydrxyl or aryl group, etc., (m) is an integer of 1-5. Thus, the durability of the magenta colored picture against the light and the moist and hot environments is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a pyrazoloazole magenta coupler and a specific color image stabilizer that is particularly effective in improving the lightfastness of dye images formed by this coupler. This invention relates to a silver halide color photographic light-sensitive material in which the following are combined.

(Prior art) By color-developing a silver halide color photographic light-sensitive material, the oxidized aromatic primary amine color developing agent and the coupler react to produce indophenol, indoaniline, indamine, azomethine, phenoxazine, etc. It is well known that phenazine and similar dyes can be produced to form color images.

In the past, most of the magenta image-forming couplers that have been put into practical use and have been studied are mostly 5-pyrazolones. Dyes formed from 5-pyrazolone couplers have excellent fastness to heat and light, but 430
There is an unnecessary absorption with a yellow component near nm,
It was known to cause color turbidity.

Pyrazolobenzimidazole bone core has long been described in British Patent No. 1,047°612 as a magenta color image forming coupler bone core that reduces this yellow component, and U.S. Patent No. 3
, 770,447, or the pyrazolotriazole bone core described in US Pat. No. 3,725.067.

The present inventors used imidazo (1,2-b) pyrazole cheek, pyrazolo'CL, 5-b) (1°2.4) triazoles, pyrazolo (1 , 5-d) Tetrazoles,
We have developed pyrazoloazole magenta couplers of pyrazolo(1,5-d)benzimidazoles and pyrazolopyrazoles.

(The first problem that the invention seeks to solve is that the azomethine dye formed from such a pyrazoloazole magenta coupler has relatively low fastness to light and heat, and furthermore, the color fastness that is conventionally used Image stabilizers (e.g. alkyl-substituted hydroquinones)
It was found that this method could not sufficiently prevent this discoloration.

An object of the present invention is to provide a silver halide color photographic material in which the fastness to light and heat of a magenta color image formed from a pyrazoloazole coupler represented by the general formula [I] below is improved.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a pyrazoloazole coupler represented by the following general formula [I]. This was achieved by incorporating a compound that

That is, the present invention provides a silver halide characterized by containing at least one pyrazoloazole coupler represented by the following general formula (II) and at least one compound represented by the following general formula (II). It is a color photographic material.

General formula [1] (wherein, R8 represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, and Z represents a group containing R represents a group of nonmetallic atoms necessary to form a nitrogen heterocycle
A dimer or higher multimer may be formed via 1 or X, or a dimer or higher multimer may be formed via a substituent bonded to the nitrogen-containing heterocycle formed by Z. may be formed.

The nitrogen-containing heterocycle formed by Z is preferably a 5-membered ring, and may be further fused with a benzene ring or the like.

-Flow formula (R3 (wherein R-value is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group,
It represents an aryloxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfone group, a cyano group, a heterocyclic group/5dooxy group, or an aryl group. m is 1
represents an integer from 5 to 5, and when m is 2 or more, each R2
1 may be the same or different (and when they are in the ortho position, they may be bonded to form a closed ring.)
At least one compound represented by the following general formula (II[)
By including more seeds, the effect was dramatically increased and the purpose was achieved even more effectively.

represents an o group, an amino group, a heterocyclic group, an acylamino group, or a halogen atom, n represents an integer from 1 to 5,
When n is 2 or more, each Ro may be the same or different, and when they are in the ortho position, they may be bonded to each other to form a closed ring. Also, when R3 is substituted at the ortho position of -〇Rs+, 10! lff and R3g may be bonded to each other to form a ring closure. ) Hereinafter, the present invention will be explained in detail.

The bilacisazole coupler used in the present invention is preferably represented by the following general formula (Ia).

(In the formula, Rs+ represents an alkyl group or an aryl group. R32 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, an aryl group. In the formula (Ia), R represents a hydrogen atom or a substituent, 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 are methine, substituted methine, =N- or -NH-
, one of the Za-Zb bond and the Zb-Zc bond 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. Furthermore, R or X may form a multimer of 21 or more bodies, and Za, Z
When b or Zc is a substituted methine, it also includes the case where the substituted methine forms a multimer of 21 or more bodies.

In general formula CI), multimer means one having two or more groups represented by general formula [I] in one molecule, and also includes bis forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by the general formula [I] (preferably one having a vinyl group,
A homopolymer consisting only of a vinyl monomer (hereinafter referred to as a vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene monomer that does not couple with the oxidation product of an aromatic-grade amine developer.

-FIQ The compound represented by formula (Ia) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is usually collectively referred to as azapentalene. It has a chemical structure. General formula (I
Among the couplers represented by a), preferred compounds are I
H-imidazo[1,2b]pyrazoles, IH-pyrazolo(5,1-c)(1,2,4))lyazoles, IH
-pyrazolo(1,5-b) pyrazoles, IH-pyrazolo(1,5-bl [1,2,4)l-lyazoles, IH-pyrazolo(1,5-d) tetrazoles and I
H-hirazolo(1,5-a)benzimidazoles, each having the general formula (r-1), (1-2], (1-3)
), (1-4), (1-5) and (1-6).

Particularly preferred among these are compounds (1-1) and (I
-3) and (1-4).

(,1-5) (f-6) Substituents Ri, Rs of general formulas (1-1) to (1-6)
and R4 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group , anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group,
Alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group, or a group bonding to carbon at the coupling position via an oxygen atom, nitrogen atom or sulfur atom, and represents a group that performs coupling/decoupling.

The case where Rz, Rs, Ra or X becomes a divalent group and forms a bis body is also included. Also, general formula (1-1)
When the moiety represented by ~(+-6) is present in the vinyl monomer, Rt, R, or R4 represents a simple bond or linking group, and through this, general formula (T-1) ~( 1
-6) and the vinyl group are bonded to each other.

More specifically, R2, R3 and R4 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group,
Trifluoromethyl group, tridecyl group, 3-(2,4-
di-L-amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g., phenyl group, -t
-butylphenyl group, 2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g. 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2- benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2
-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocycle Oxy group (e.g., 2-benzimidazolyloxy group, etc.)
, acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (
(e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamide group, benzamide group, tetradecanamide group, α-(2°4-di-amylphenoxy)butylamide group, γ-(3-t-butyl- 4
-hydroxyphenoxy)butyramide group, α-[4-
(4-hydroxyphenylsulfonyl) phenoxy) decanamide group, etc.), anilino group (e.g. phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5=dodecyloxycarpol) Anilino group, N-acetylanilino group, 2
-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N, N dibutylureido group, etc.), imido groups (e.g., N-succinimide group, 3-penzylhydantoynyl group, 4-(2-ethylhexanoylamino)
phthalimide group, etc.), sulfamoylamino group (e.g. Eva, N, N-dipropylsulfamoylamino group, N-
methyl-N-decylsulfamoylamino group, etc.), alkylthio groups (e.g., methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group,
3-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), arylthio group (e.g., phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group) group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g., 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino L2.4-di-t-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g.,
methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.)
, carbamoyl group (e.g., N-ethylcarbamoyl group, N.

N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-<3-(2゜4-di-monoamylphenoxy)propyl)carbamoyl group, etc. ), acyl groups (e.g. acetyl group, (2,4-di-t-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl groups (e.g. N-ethylsulfamoyl group, N
, N-dipropylsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N
-dodecylsulfamoyl group, N,N-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octane sulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g. octane sulfamoyl group, etc.) sulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), ryoroxycarbonyl group (e.g., phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), and X represents a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxyl group, or a group connected by an oxygen atom. (
For example, acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group,
Ethoxyoxaloyloxy group, pyruvinyloxy group,
Cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4
-methanesulfonylphenoxy group, α-naphthoxy group,
3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group,
2-benzothiazolyloxy group, etc.), groups linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2345.6-pentafluorobenzamide group, octane Sulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, 1
-piperidyl group, 5,5-dimethyl-24-dioxo-
3-oxazolidinyl group, 1-hensyl-ethoxy-3
-hydantoinyl group, 2N-1,1-dioxo-3(2
H)-oxo-1,2-'benzisothiazolyl group, 2
-oxo-12-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3.5-diethyl-1°24
-triazol-1-yl, 5- or 6-furomobenzotriazol-1-yl, 5-methyl-1,2,3
, 4-) lyazol-1-yl group, benzimidazolyl group, 3-hensyl-1-hydantoynyl group, ■-benzyl-5-hexadecyloxy-3-hydantoynyl group,
5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-
hydroxy-4-propanoylphenylazo group, etc.), groups linked via a sulfur atom (e.g., phenylthio group, 2-
Carboxyphenylthio group, 2methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2
-butoxyphenylthio group, 2-(2-hexanesulfonylethyl)-5-t-octylphenylthio group, benzylthio group, 2-cyanoethylthio group\1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3 ，
4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-5-thiophenylthio group, 2
-phenyl-3-dodecyl-1,2,4-triazolyl-5-thio group, etc.).

When Rz, Rx, R4 or .10 decylene group, CHtCH
zOCHzCHz-1, etc.), a substituted or unsubstituted phenylene group (for example, 1°4-phenylene L1.3-phenylene group, N1ICo-Rz-CONII- group (R3
represents a substituted or unsubstituted alkylene group or phenylene group.

When those represented by general formulas (T-1) to (1-6) are present in the vinyl monomer, the linking group represented by R, R, or R4 is an alkylene group (substituted or unsubstituted). alkylene group, for example, methylene group, ethylene group, 1
．． 10-Decylene group, CIhCHzOCHzCtlx-
etc.), phenylene group (substituted or unsubstituted phenylene group, such as 1,4-phenylene Ll, 3-phenylene group, -C0NII-10-OCO) and aralkylene group (including groups formed in combination, for example).

The vinyl group in the vinyl monomer has the general formula (1-1
) to (1-6) may have substituents other than those represented. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide,
n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, L-butylacrylate, iso-butylacrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
lauryl acrylate, methyl methacrylate, ethyl acrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylenebisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic Group vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride. acid,
Maleic acid ester, N-vinyl-2-pyrrolidone, N
-vinylpyridine, and 2- and 4-vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas (1-1) to (1-6) above are described in the documents listed below.

The compound of general formula (1-1) is disclosed in JP-A No. 59-16254.
No. 8, etc., the compound of general formula CI-2') is disclosed in JP-A No. 6
0-43659, etc., the compound of the -catalytic formula (1-3) is described in Japanese Patent Publication No. 47-27411, etc., and the compound of general formula (1-4) is described in Japanese Patent Publication No. 59-171956 and 60-17.
2982, etc., the compound of general 2(1-5) is disclosed in JP-A-60-33552, etc., and the compound of formula -11 (+-6) is disclosed in U.S. Patent No. 3,061,432, etc. Each is listed.

Also, JP-A-58-42045, JP-A-59-1775
No. 54, No. 59-177553, No. 59-17755
The highly color-forming ballast groups described in No. 4 and No. 59-177557 have the above general formulas (1-1) to (1-
This applies to any of the compounds in 6).

Among the compounds represented by the general formulas (1-1) to [I-3] and (1-4), a branched alkyl group as described in JP-A No. 61-65245 is used as the Pyrazolotriazole couplers directly linked to the 3 or 6 position, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254; Pyrazoloazole couplers with alkoxyphenylsulfonamide ballast groups such as European Patent Application Publication No. 226
, 849, pyrazolotriazole couplers having an alkoxy group or aryloxy group at the 6-position, or an alkyl or arylsulfonylalkyl group as represented by the monocatalytic formula (XI) in JP-A No. 61-275842. Couplers in the 3-position of the pyrazolotriazole ring are preferred.

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

(M-3) (M-5) (M-6) (M (M-13) (M-15) (M-17) (M-21): y÷50:50 (weight ratio, same below) N = N x:y=50:50 x:y=40:60 , preferably from 1 x 102 mol to 5 x 10-' mol.

The color image stabilizer represented by the general formula [■] used in the present invention will be explained in detail below.

General Formula (n) In General Formula (II), R21 is a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine), an alkyl group (e.g. methyl, butyl, t-octyl), an alkoxy group (
For example, methoxy, butoxy, dodecyloxy, hexyloxyethoxy, 2-ethylhexyloxy), alkylthio groups (e.g. methylthio, 2-ethylhexylthio), amino groups (e.g. N,N-dibutylamine,
N-2-ethylhexylamino, N-ethoxyethoxy), acylamino groups (e.g., acetamide, henzamide, tetradecanamide, α-(2,4-di-t-amylphenoxy)butyramide), sulfonamide groups (e.g., methanesulfone) amide, octanesulfonamide, N-octyl-methanesulfonamide), alkoxycarbonyl groups (e.g., ethoxycarbonyl, dodecyloxycarbonyl), aryloxycarbonyl groups (e.g., 4-L-octylphenoxycarbonyl, 4-acetamidophenoxycarbonyl) , acyl groups (e.g. acetyl, tetradecanoyl), carbamoyl groups (e.g. N,N-dibutylcarbamoyl, N-dodecylcarbamoyl), sulfamoyl groups (e.g. N,N-dibutylsulfamoyl, N-2-ethyl hexylsulfamoyl), sulfonyl group (e.g. methylsulfonyl, octylsulfonyl), cyano group, heterocyclic group (e.g. 4-morifolinyl, 1-piperazinyl, 1-piperidinyl, l-pyrrolidinyl), bitroxy group or Represents a radical group (eg, phenyl, naphthyl).

As RZ+, the above-mentioned substituents are particularly preferred.

m represents an integer from 1 to 5, and when m is 2 or more, each R21 may be the same or different, and when they are in the ortho position, they may be bonded to form a closed ring. (
For example, substituents at the ortho positions combine with each other to form a 2,3-methylenedioxybenzene ring, an 8-chromanyl ring, etc.) Below, specific examples of compounds of the general formula (IH) used in the present invention are shown, It is not limited to these (S-
1) (S-2) NIICOC+ lIf□3 l OC+2■gs SC+2■zs (S-7) (S-11) CZ ++ 5 (S-13) (S-14) COC+Jzs C 1lzs (S-9) CC+1lht (S 15] (S OCall+t 1st) (S-19) (S-20) zHs 0CIII+ to GO? (S-25) Cwt(s (S-27) (s II to T-1 (S-21) shiaH+3 (tJ shi6H13[1) The compound represented by general formula (II) is used in an amount of 0.5 to 200% by weight, preferably 2 to 150% by weight based on the coupler, although it varies depending on the type of coupler used in combination. It is appropriate to use the amount within this range. If it is less than this range, the effect of preventing color fading is extremely small and is not suitable for practical use. If it is too much, the progress of development may be inhibited and the color density may decrease.

The compound of general formula (II) of the present invention is disclosed in Japanese Patent Publication No. 61-160
It can be synthesized according to the method described in No. 63.

Next, preferred embodiments of the color image stabilizer represented by the general formula (Ill) will be described in detail below.

In the formula, R31 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl, propyl,
n-butyl, i-butyl, n-octyl. -dodecyl, n-hexadecyl, cyclohexyl), or an aryl group having 6 to 20 carbon atoms (eg, phenyl, naphthyl).

R3g is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl, naphthyl, t-
hexyl, L-octyl, 5eC-dodecyl, n-hexadecyl, cyclohexyl), aryl groups having 6 to 20 carbon atoms (e.g. phenyl, naphthyl), alkoxy groups having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, n-butoxy, i-butoxy, n-octyloxy, n-hexadecyloxy), alkylthio groups having 1 to 20 carbon atoms (e.g. methylthio, n-butylthio, n-octylthio),
Arylthio groups having 6 to 20 carbon atoms (e.g. phenyl, naphthylthio), amino groups (e.g. NN-dimethylamino, N,N-dioctylamino, N-octylamino),
Heterocyclic group (e.g. 4-morpholinyl, l-piperazinyl, 1-piperidinyl, 1-pyrrolidinyl), carbon number 1
~20 acylamino groups (e.g. acetylamino, propionylamino), halogen atoms (e.g. eva, chloro, brome). n represents an integer from 1 to 5, and n is 2
In the above cases, each R3□ may be the same or different, and when they are in the ortho position, they are bonded to each other to form a 5- or 6-membered ring (for example, a chroman ring, a spirochroman ring, a spiroindane ring, The ring may be closed with a coumaran ring).

In addition, when R1 is substituted at the ortho position of -0R11, -0R81 and 0R3t are bonded to each other and the 5- or 6-membered ring (
For example, a chroman ring or a coumaran ring) may be formed. Here, among the groups represented by R31 and R3''2, the group partially containing alkyl or aryl may be further substituted with a substituent.

Preferred substituents include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an acylamino group, a hydroxyl group, a halogen atom, a cyano group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an acyloxy group. , nitro groups, etc.

The compound of general formula (III) above may be a dimer or more.

Specific examples of the compound represented by the general formula (lI[) are shown below, but the invention is not limited thereto.

CI+.

υshii1 A-22 A-25 LIL;
No. 60.589, No. 4,273,864, Japanese Unexamined Patent Publication No. 5
No. 5-50244, No. 53-20327, No. 53-7
No. 7526, No. 59-10539, Special Publication No. 57-37
No. 856, JP-A-62-157031, JP-A No. 63-95
No. 448, No. 63-95446, No. 62-27353
No. 1, No. 62-244045, No. 62-244046
It can be easily synthesized by the method described in No. 1, etc., or according to that method.

The compound of general formula (III) of the present invention differs depending on the type of coupler used in combination, but the compound has 0.
It is appropriate to use it in a range of 5 to 200% by weight, preferably 2 to 150% by weight. If the amount is less than this range, the effect of preventing color fading is extremely small and is not suitable for practical use. On the other hand, if the amount is too large, the progress of development may be inhibited, leading to a decrease in color density.

The coupler of the present invention is I! per mole, from 2 x 10-2 mol to 5 x 10-' mol, preferably lXl0-
2 moles to 5 x 10-' moles are added.

Two or more types of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers.
Of course you can.

Furthermore, when carrying out the present invention, two or more compounds represented by the -a formula (II) can be used in combination, and preferably, a compound represented by the general formula (f[I) is further used in combination. In this case, two or more compounds represented by the general formula (II[) can be used in combination, and Ike's known antifading agent can also be used in combination.

Known anti-fading agents include hydroquinones, phenols, hindered amide polycomplexes, amines, chromanols, coumarans, etc.
No. 3162, No. 5B-24141, No. 52-1522
No. 25, U.S. Pat. No. 3,698,909, U.S. Pat. No. 4,268,593
British Patent No. 2069162(A), British Patent No. 202773
No. 1, JP-A-61-72246, JP-A No. 62-27095
No. 4 and No. 61-189540.

As a known anti-fading agent, combination use with a compound represented by the following formula [IV] is particularly preferable in order to further enhance the effects of the present invention.

(In the formula, W represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring, and A represents a hydrogen atom, an alkyl group, an aryl group, a heterocycle, an acyl group, a sulfonyl group, a sulfinyl group, an oxyradical group, hydroxy group, alkoxy group, substituted or unsubstituted amino group.

The ring formed by W may further have a substituent, and may form a spiro ring, a bicyclo ring, or a fused ring. Furthermore, A and W may be combined with each other to form a ring. ) Specific examples are shown below.

(B (B (B-8) (B-3) (B-10) CB-4) (B-5) (B (B (B-7) (B-14) IJ2S (B (B-21) (B (B (B (B-18) (B-23) (B-19) (B-20) (B-9) (B-11) (B (B +13 (B-25) (B- 26) (B-27) (B-28) (B-29) (B-30) (B-31) In addition to these, JP-A-61-260247, JP-A-61-61
-72246, 62-24255, 62-25
No. 757, No. 62-205350, No. 62-2709
No. 54, No. 62-270955, No. 62-27855
No. 0, No. 62-278551, No. 62-279335
No. 62-279339, No. 62-297847, No. 62-297848, No. 63-13040, No. 63-38940, No. 63-40153, No. 63-
No. 43145, No. 63-43146, No. 638241
No. 4, No. 63-82415, No. 63-95447,
No. 63-94239, No. 63-95442, No. 63
-95443, 6395444, 63-986
No. 62, No. 63-101848, No. 63-10184
No. 9, No. 63-115167, No. 63-148260
No. 63-149624, No. 63-149643, No. 63-149644, No. 63-149645,
Antifading agents described in specifications such as No. 63-149646 may be used in combination.

General formulas (1), (Il) and (II) used in the present invention
The compound I) can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a Latin lath dispersion method, and more preferably an oil-in-water dispersion method. can. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution.

Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion,
Further, if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, etc. before use for coating.

- Compounds of the limiting formulas (n) and (III) may be used in a green-sensitive silver halide emulsion layer containing a pyrazoloazole coupler of general formula (N) or its adjacent layer (an intermediate layer between a red-sensitive layer and a green-sensitive layer and/or It is also preferable that the compounds of general formulas (1), (n) and (■) are co-emulsified by the above-mentioned oil-in-water dispersion method to provide a high It is preferably dispersed in the green-sensitive silver halide emulsion layer as a fine particle dispersion in a boiling point organic solvent.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, trinonyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (2-ethylhexyl phenyl phosphate, etc.), -Ethylhexylhenshade, dodecylbenzoate, 2-
ethylhexyl-p-hydroxybenzoate, etc.),
amides (diethyltoticanamide, N-tetradecylvirolitone, etc.), alcohols or phenols (
Isostearyl alcohol, 2.4-'di-tert-
amylphenol, etc.), aliphatic carboxylic acid esters [
(Dioctyl azelate, dioctyl sebacate, glycerol tributyrate, isostearyl lactate,
trioctyl citrate, etc.), aniline derivatives (N,
N-dibutyl-2-butoxy-5-tart-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexane. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat.
, No. 541, 230, etc.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

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. Although particles with crystal defects such as twin planes or composites thereof may be used, it is preferable to use regular particles.

The grain size of silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. However, it is preferable to use a monodisperse emulsion.

As a monodisperse emulsion, the average grain diameter is about 0. Silver halide grains larger than 1 micron, of which at least 95
Emulsions in which the weight percent is within ±40% of the average grain diameter are typical. The average particle diameter is between 0.25 and 2 microns and at least 95% by weight or at least 95% by number
It is preferable to use an emulsion in which the percentage of silver halide grains is within a range of ±20% of the average grain diameter.

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such processes is Research Disclosure Nα176.
43 and Circulation, 18716.

Various color couplers can be used in combination with the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-C. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, agenta and cyan)
It is important to have a coupler that gives a color development property of
7643, ■-C and D can be used.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, N (page 28 of 117643 and ibid., N.

18716, from the right column on page 647 to the left column on page 648.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, 1
la17643 pages 28-29 and the same, k18716
651, 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, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. The present invention also relates to Research Disclosure 17123 (197
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in J.

[Example] The present invention will be described below based on specific examples, but is not limited thereto.

Example 1 Magenta coupler 1-(2,4,6-1-lichlorophenyl)-3-N2-lytetra-5-tetradecanamido)anilino)-4-(2-butoxy5-tert-octylphenylthio)- 2-pyrazolin-5-one (a
) 10 g of tricresyl phosphate in 20 ml of 1. and 20 ml of ethyl acetate, and this solution was mixed with 1% sodium dodecylbenzenesulfonate (aqueous solution) by volume. ffl
The mixture was emulsified and dispersed in 80 g of gelatin solution containing 8 d.

Next, this emulsified dispersion was mixed into a green-sensitive silver chlorobromide emulsion (Br
50 mol %) (contains 7 g of Ag), sodium dodecylbenzenesulfonate was added as a coating aid, and the mixture was coated on a paper support laminated on both sides with polyethylene.

The amount of coupler applied was set at 400 μ/Po. A gelatin protective layer (gelatin Ig/n()) was applied on top of this layer to prepare sample IA.

In a similar manner, when preparing the above emulsified dispersion, the coupler of the general formula (1) of the present invention, the compound of the general formula CII) of the present invention, ([[I) and the comparative compound as shown in Table 1] I created a combination of Sample IB-IU was prepared by adding 50 mol % of the compound of general formula (II) (1) and the comparative compound to the coupler used, and coating in the same manner as sample LA except for changing the coupler and inhibitor.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

Processing process: 1 degree U-tube color development
Bleach fixing at 37"C for 3 minutes and 30 seconds Washing with water at 33°C for 3 minutes Drying at 70 to 80°C for 1 minute The composition of each processing solution is as follows.

left i two anti-image diethylene triamine pentaacetic acid nitrilotriacetic acid henzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl 4-aminoaniline sulfate bitroxyl Amine sulfate optical brightener (WHITEX4B Add water to pH (25°C) 1 town foot 1 Namizu 00m 1, 0g 2, Og 15 relatives 0d 2.0g 1, 0g 0g 4, 5g 3.0g 000d 10゜00d Ammonium thiosulfate (70wtχ) 150d Sodium sulfite 18g Iron(III) ethylenediaminetetraacetate Ammonium 55g Disodium trilamin ethylenediaminetetraacetate 5 Add water 1000 relative pH (25°c)
6.70 Attach a Fuji Film ultraviolet absorption filter that cuts wavelengths of 400 nm or less to each sample on which a dye image has been formed in this way, and use a xenon tester (
A fading test was conducted for 6 days at an illuminance of 200,000 lux. The measurement was carried out using a Macbeth densitometer RD-514 model (Status AA filter), and changes in concentration were measured at the initial concentration of 2.0. The results are shown in Table 1.

Comparative magenta coupler (a) Comparative compound (A) Comparative compound (B) Compound described in JP-A-59-125732 From these results, the compound represented by the general formula (II) of the present invention has an excellent light fastness improving effect. It can be seen that the light fastness improvement effect is more excellent than expected compared to the 5-pyrazolone type. Furthermore, it can be seen that when used in combination with -1 formula (III), the effect is remarkable, and compared to the case where comparative compound (A) or CB) is added, the light fastness is significantly improved.

The same effect as above was obtained even when M-4 was used instead of M-12 as the magenta coupler.

Example 2 Multilayer samples (2A to 20) shown in Table 2 were prepared by the following method using M-12 as a magenta coupler. At this time, the color image stabilizer 1 in the third layer was added in an amount of 50 mol % based on the magenta coupler, and the color image stabilizer 2 and the comparative compound were added in an amount of 100 mol % based on the magenta coupler.

Silver halide emulsion (1) of the blue-sensitive silver halide emulsion layer was prepared as follows.

(1 liquid) H2O1000 relative (2'ta) (3 liquid) NaCj! gelatin Sulfuric acid (IN) Compound below (1%) L (4? night) (5 liquids) (6 nights) C.T.

Br Na CI Add H and O AgN○.

Add H, 0 and Br aCI KZ IrC1b (0° Add H, O (7 liquids) A g N O * NH, NO3 8, 8 g 5 g 20 relative 3 products 14.01 g 1.72 g 5 g 30 In1 56, 03 g 6.88g 001%) 1, 095d 00g 1 (50%) H, O were added, 285- (Liquid 1) was heated to 75°C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 40 minutes. After another 10 minutes, (liquid 6) and (liquid 7)
were added simultaneously over a period of 25 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin and adjust the pH to 6.
2, average particle size 1.01 μm, coefficient of variation (standard deviation divided by average particle size; s/d) o
, 08 Monodisperse cubic silver chlorobromide emulsion containing 80 mol% silver bromide (
1) was obtained. This emulsion was optimally chemically sensitized with triethylthiourea.

silver halide emulsion (2) of a blue-sensitive silver halide emulsion layer;
In addition, the silver halide emulsion of the green-sensitive silver halide emulsion layer (
Silver halide emulsions 3) and (4) and red-sensitive silver halide emulsion layers (5) and (6) were also prepared in the same manner by changing the amount of chemicals, temperature and addition time.

The shapes, average grain sizes, halogen compositions, and coefficients of variation of silver halide emulsions (1) to (6) are as shown below.

(1) Cube 1.01 80 0.08 (2)
Cube 0.70 80 0.07(3) Cube 0.52 80 0.08(4) Cube 0
．． 40 80 0.09(5) Cube 0.44
70 0.09 (6) Cube 0.36 7
A multilayer color photographic material having the layer structure shown below was prepared on a paper support laminated on both sides with 0.08 polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 1.91 g of color image stabilizer (Cpd-1), antifoggant (Cpd-1),
2) To 0.46g, add 27゜2cc of ethyl acetate and solvent (
Solv-1) 3. 8cc, solvent (Solv-2
) 3. 8 was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, to a 6=4 mixed emulsion of silver halide emulsion (1) and silver halide emulsion (2), 5.0% of the following blue-sensitizing dye was added per mole.
The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As the gelatin hardening agent for each layer, 1-oxy35-dichloro-3-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; 5O1 (5.0 x 10'' mol per mol of emulsion) Green-sensitive emulsion layer; To the red-sensitive emulsion layer, the following compounds were added in an amount of 2.6 x 10'' mol per mol of silver halide.

O3- 5OffH·N(Czllsh (4°oxto-' mol per mol of emulsion) and (7° per mol of emulsion) red-sensitive emulsion layer; (0°SOJ·N(CJs)z OXIO-' mol per mol of emulsion) ) 9X10"mol) For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4hydroxy-6-methyl-133a 7-titrazaindene was added at 1.2X10-"mol and 1.1Xl0-" per mole of silver halide, respectively. Mol added.

Further, 1.0.times.10@-3 mol of 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the green-sensitive emulsion layer per mol of the halogenated compound.

Furthermore, s, oxto-; mol of 2-amino-5-mercapto-13,4-thiadiazole was added to the red-sensitive emulsion layer per mol of silver halide.

A dye was also used as an irradiation prevention dye.

The composition of each layer is shown below. The numbers represent the coating amount (g/bo),
The silver halide emulsion represents the coated amount in terms of silver.

(Layer structure) and support paper support laminated on both sides with polyethylene (the polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye (ulmarine blue))] 1st layer (blue-sensitive layer) Silver halide Emulsion (1) + (2) 0.26 gelatin 1.20 yellow coupler (ExY) 0.66 color image stabilizer (C
pd-1) 0.07 anti-capri agent (Cp
d-2) 0.02 solvent (Solv-1)
0.13 solvent (Solv-2)
0.13 Second layer (color mixing prevention N) Gelatin 1.34 Color mixing prevention agent (Cpd-3) 0.04 Solvent (Sol
v-3) 0.10 solvent (Solv-4
) 0.10 Third layer (green sensitive layer) Silver halide emulsion (3) + (4) Gelatin magenta coupler (M-12) Color image stabilizer 1 Color image stabilizer 2 Stain inhibitor (Cpd-11) Stain Inhibitor (Cpd-12)? Container (Solv 3)? Container (Solv 5) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (tJV-1) Color mixing inhibitor (Cpd-2) )8 medium (Solv-2) Fifth layer (red sensitive layer) Halogenated i艮(5)+(6) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) 0, 14 1, 30 0, 27 (Table 2) 0, 025 0, 032 0, 21 0, 33 Color Image stabilizer (Cpd-1) Color image stabilizer (Cpd-7) Antifoggant (Cpd-2) Capacitor (Solv-1) 6th N (ultraviolet absorbing layer) Gelatin ultraviolet absorber (IJV-1) ? Container (Solv-2) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin (ExY) Yellow coupler 0, 17 0, 08 0, 05 0, 02 (ExC -1) Cyan coupler 0■ (Cpd-3) Color mixture prevention agent il! (ExC-2) Cyan coupler υII (Cpd-4) Color image stabilizer! (Cpd-1) Color image stabilizer average molecular weight 160 (Cpd-2) Antifoggant (Cpd-11) Anti-stain agent C511zttl (Cpd-12) Anti-stain agent (UV ■) Ultraviolet absorber (Cpd-7) Color 4:2:5 mixture (weight ratio) of image stabilizer; 12:10:3 mixture (weight ratio) (Solv-1) Solvent CaH+t-Cll-CH-←C1h→-tcOOc@
Htv\0/ (Solv-2) Solvent 0=P÷0-C9 H+*'is.

) co(Solv-3) solvent (Solv-4) solvent These results show that the color image stabilizer of the present invention has an excellent effect of improving light fastness, and furthermore, when used in combination with the compound represented by general formula (II), the color image stabilizer of the present invention has a remarkable effect of improving light fastness. It can be seen that the robustness is improved.

Similar effects were obtained when M-4 was used instead of M-12 as the magenta coupler.

(Solv-5H container) The above photosensitive material was exposed through an optical wedge and then processed in the same manner as in Example 1.

Each sample with a dye image formed in this way was attached with a Fuji Film ultraviolet absorption filter that cuts wavelengths of 400 nm or less, and exposed to light for 4 weeks in a fluorescent lamp bleacher (1.5 million lux) to perform a color fading test. The density change in the density portion with an initial density of 1.0 was measured. The results are shown in Table 2.

Example 3 Multilayer samples (3A-3) shown in Table 3 were made by the following method. At this time, color image stabilizer 1 in the third layer was added in an amount of 50 mol % based on the magenta coupler, and color image stabilizer 2 and the comparative compound were added in an amount of 100 mol % based on the magenta coupler.

Silver halide emulsion (1) of the blue-sensitive silver halide emulsion layer was prepared as follows.

(1 solution) (4 solutions) (5 solutions) (6 solutions) (2 solutions) Sulfuric acid (IN) (3 solutions) The following compounds (1%) H3 0cc cc H5 (7 solutions) (1 solution) at 60 It was heated to 'C, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 60 minutes. Ten minutes after the completion of addition of (liquid 4) and (liquid 5), (liquid 61) and (liquid 7) were added simultaneously over a period of 25 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.0, average particle size 1.0 μm, coefficient of variation (standard deviation divided by average particle size; s/d) 0.11, silver bromide 1 mol% A monodisperse cubic silver chlorobromide emulsion was obtained. Triethylthiourea was added to this emulsion to perform optimal chemical sensitization. Furthermore, the following spectral sensitizing dye (Sen-1) was added to silver halide emulsion 1.
7X10-' moles were added per mole.

Silver halide emulsion (2) in the green-sensitive silver halide emulsion layer and silver halide emulsion (3) in the red-sensitive silver halide emulsion layer.
) were also prepared in the same manner as above by changing the amount of chemicals, temperature, and addition time.

A spectral sensitizing dye (Sen) was added to silver halide emulsion (2).
-2) was added at 5X10-4 mol per mol of emulsion, and spectral sensitizing dye (Sen) was added to silver halide emulsion (3).
-3) was added in an amount of 0.9 XLO-' mol per mol of emulsion.

The shapes, average grain sizes, halogen compositions, and coefficients of variation of silver halide emulsions (1) to (3) are as shown below.

(1) Cube 1.00 1.0 0.11 (2)
Cubic 0.45 1.0 0.09 (3) Cubic 0.34 1.8 0.10 (Sen-1) SOI (Sen-3) Using the prepared silver halide emulsions (1) to (3) A multilayer color photographic window optical material with the layered structure shown below was prepared.

The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY) was added to 2 ml of ethyl acetate to prepare the coating solution for the first layer.
7.2 cc and 3.8 cc of solvent (Solv 1) were added and dissolved, and this solution was mixed with 18% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 5 cc. On the other hand, silver halide emulsion (1)
5.0 blue-sensitive sensitizing dye (Senl) per mole of silver
A sample containing X10-' moles was prepared. The above-mentioned emulsified dispersion and this emulsion layer were mixed and dissolved to prepare a coating solution i having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

The gelatin hardening agent for each layer is 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

For the red-sensitive emulsion layer, the following compound was added in an amount of 1.9×10 −' moles per mole of silver halide.

Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added to the blue-sensitive emulsion layer in an amount of F) 1 ,Ox 1 Q-'' mol per mol of silver halide.

In addition, 1-(5
-methylureidophenyl)-5-mercaptotetrazole at 1.0X1 per mole of Il halide, respectively.
0-3 mole 1.15X10-3 mole was added.

Further, 2.5×10 −' mol of 2-amino-5-mercapto-1,3,4-thiadiazole was added per mol of chloride to the red-sensitive emulsion layer.

The composition of each layer is shown below.

(N configuration) Paper support laminated on both sides with polyethylene support (No.-Ji
White pigment: TiO□ (2.7g/
Layer 1 (blue-sensitive layer) Silver halide emulsion (1) 0.26 Gelatin 1.13 Yellow coupler (ExY) 0.66? Container (Solv
-1) 0. 28 Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-1) Solvent (Solv-1) Solvent (Solv-2) Dye (T-3) Third layer (green-sensitive layer) Silver halide emulsion (2 ) Gelatin magenta coupler (Table 3) Color image stabilizer 2 Anti-stain agent (Cpd-4) Anti-stain agent (Cpd-5) Solvent (Solv-2) Solvent (Solv-3) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-1) 0, 89 0, 08 0, 20 0, 20 0.005 0, 15 0, 51 0, 27 0.025 0.032 0, l 9 0, 15 1, 42 0, 52 0, 06 Solvent (Solv-4) Dye (T-2) Fifth N (red-sensitive layer) Silver halide emulsion (3) Gelatin cyan coupler (ExC-1) (ExC -2) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) ? Each section (Solv-4) Solvent (Solv-5) Solvent (Solv-6) Sixth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-4) Solvent (Solv-4) Dye (T-2) Seventh layer (Retaining layer) Gelatin polyvinyl alcohol acrylic 0, 260, . 0 1 5 0, 22 1.06 0, 16 0, 13 0, 32 0, 18 0, l 0 0, 10 0, 11 0, 48 0, 18 0, 08 0.005 1, 33 Modified copolymer (Degree of modification 17%) 0.05 Liquid paraffin 0.03 The relationship between the symbols of the above additives in this example and those in Example 2 is as follows.

1 茄” - Disaster Raid ExY ExY cM-t Cpd-3 , -6-1 UV-I UV-1 Solv -I 5olv -41-2〃-
3 // -3/J -5 〃-4〃-2 T-2T-2 The symbols of other additives have the following structural formulas.

(ExC-1) Cyan coupler (Solv-6) solvent L (T-3) (ExC-2) Cyan coupler (Solv-5) solvent COOCHt CHCs Hq (CHz )s Cz Hs COOCHz CHC-H9 tHs The above photosensitive material was exposed through an optical wedge and processed in the following steps.

<Processing temperature>Temperature> Color development 35°C Bleach fixing 35°C Washing with water ■ 35°C Washing with water ■ 35°C Washing with water ■ 35°C Drying 75°C Processing time> 45 seconds 45 seconds 30 seconds 30 seconds 30 seconds 60 seconds exposure time 1 liquid water ethylenediamine-N5 N,N',N'-tetramethylenephosphonic acid triethanolamine sodium chloride potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl- 4-Amine aniline sulfate 5°N, N-bis(carboxymethyl)hydrazine 5°Fluorescent brightener (UVITEX CK manufactured by Ciba Geigy) 1. Add 0 g water 1000d pH (25°C) In constant JLIII Water mother liquor 3,0g 8,0g 1,4g 5g 0g 0g io,os 00d Replenisher 3,0g 2g 0.3g 5g 7゜0g 6゜0g 2゜0g 10.35 700ad! Ammonium thiosulfate solution (700g/l) 100ml ammonium sulfite 18g ethylenediaminetetraacetic acid ferric ammonium dihydrate 55g ethylenediaminetetraacetic acid disodium salt 3g ammonium bromide 40g glacial acetic acid
Add 8g water
10001dpH (25'C)
5.5 Washing liquid Use tap water that has been treated with an ion exchange resin to reduce calcium and magnesium levels to 3 ppm or less. (25°
The conductivity at C was 5μ57cm. ) A Fujifilm ultraviolet absorption filter that cuts wavelengths below 400 nm was attached to the sample prepared in this way, and a fluorescent light fader (1,
50,000 lux) for 6 weeks to perform a fading test.
The concentration change was measured at an initial concentration of 2.0. The results are shown in Table 3.

These results show that the color image stabilizer of the present invention exhibits an excellent effect of improving light fastness, and furthermore, when used in combination with the compound represented by the general formula [■], the light fastness is significantly improved.

Example 4 M-4, M-5, M9, M-11 was used instead of magenta coupler M-.12 or M-11 in the third layer of Example 3.
, M-18 was conducted in the same manner as in Example 3, and as in Example 3, the compound of the present invention showed an excellent effect of improving light fastness.

〔Effect of the invention〕

As can be seen from the Examples, magenta images obtained by processing the silver halide color photographic material of the present invention exhibit significantly high fastness to light.

Display of incidents name of invention person who makes corrections Relationship with the incident 1971 Patent Application No. 1734171 Silver halide color photographic material

Claims (1)

[Claims] (1) A silver halide color photographic photosensitive material containing at least one pyrazoloazole coupler represented by the following general formula [I] and at least one compound represented by the following general formula [II] material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or Represents a group that can be separated, and Z represents a nonmetallic atom group necessary to form a nitrogen-containing heterocycle. A dimer or higher multimer may be formed via R_1 or A dimer or higher polymer may be formed through a substituent bonded to the nitrogen-containing heterocycle.General formula [II] ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a cyano group,
Represents a heterocyclic group, hydroxy group or aryl group. m represents an integer from 1 to 5, and when m is 2 or more, each R_2_1 may be the same or different, and when they are in the ortho position, they may combine to form a ring. . )