JPS6319850B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic material,
In particular, the dye efficiency is high in the color development process,
In addition, the photographic properties are not affected by changes in the pH of the color developing bath (that is, the processing stability is improved), and the color fading and non-coloring areas (hereinafter referred to as white areas) of the dye image finally obtained by the development process are improved. This invention relates to a color photographic material with improved discoloration. Various pyrazolone derivatives are known as magenta dye-forming couplers (hereinafter referred to as "magenta couplers"). However, the pyrazolone derivatives commonly used in photographic materials are four-equivalent couplers. That is, in order to react with an aromatic primary amine color developing agent and form 1 mole of dye, development with 4 moles of silver halide as an oxidizing agent is theoretically required. In contrast, pyrazolones having an active methylene group substituted with a group that oxidatively couples with the oxidation product of an aromatic primary amine developer require only 2 moles of silver halide to be developed. Moreover, the four-equivalent pyrazolone derivatives have a high color development efficiency (conversion rate of coupler to dye).
Usually, only about 1/2 mole of dye is formed per mole of coupler. As a method for reducing the amount of silver halide required for development and improving color development efficiency, a method using diequivalent pyrazolone type magenta couplers has been proposed for a long time. As a pyrazolone derivative that leaves an oxygen atom, for example, a compound having an aryloxy group at the 4-position of 5-pyrazolone is disclosed in US Pat. No. 3,419,391.
Compounds having an acyloxy group are described in US Pat. No. 3,311,476 and US Pat. No. 3,926,631. All of these require complicated synthesis steps to synthesize the desired product, making the final two-equivalent magenta coupler extremely expensive. It has the disadvantage that the manufacturing cost is not reduced much. As a pyrazolone derivative that leaves a nitrogen atom, for example, an imidazolyl group at the 4-position of 5-pyrazolone,
Compounds having pyrazolyl groups, triazolyl groups, etc. are described in US Pat. No. 4,076,533 and US Pat. No. 4,241,168. Synthesizing these couplers requires two to four steps starting from a four-equivalent coupler with no substitution at the coupling active site, and the cost of the couplers is still high. Moreover, some compounds are unstable or have slow coupling reactions with oxidation products of aromatic primary amines, impairing photographic performance. On the other hand, as pyrazolone derivatives that release a sulfur atom, for example, a compound having a heterocyclic thio group or an arylthio group at the 4-position of 5-pyrazolone is disclosed in U.S. Patent No. 3227554, and a compound having a thiocyano group is disclosed in U.S. Patent No. 3214437. No. 4,032,346 describes compounds having dithiocarbamate groups. These compounds have the advantage that they can be synthesized in most cases in one step from four-equivalent pyrazolones, but when incorporated into silver halide photosensitive materials, they are almost always released during the development process. Mercapto compounds interact with silver halide to inhibit development,
The compound is extremely unstable, making it difficult to use it for anything other than special purposes. The inventors of the present invention have conducted various studies in search of a coupler that is inexpensive to manufacture, has excellent photographic performance, and has improved coloring efficiency by reducing the amount of silver halide by half, which is an essential advantage of two-equivalent magenta couplers. As a result, it was found that a compound having a 2-alkoxyarylthio group at the 4-position of 5-pyrazolone specifically has excellent performance among arylthio splitting couplers. Moreover, surprisingly, the light fastness of the magenta color image formed from the ordinary coupler having an arylthio group is extremely low, whereas the magenta color image formed from the pyrazolone coupler used in the present invention is resistant to light. It is also robust. Needless to say, performance requirements for assembling a color photographic material include excellent development processability and resistance to fading. In particular, it is important to minimize fading of dye images and discoloration of white backgrounds. 4-, which has the excellent specific properties already mentioned.
(2-alkoxyarylthio)-5-pyrazolone couplers, but it is very important to further significantly improve the fading and discoloration of white background, so the inventors of the present invention have developed various anti-fade and anti-stain agents. As a result of using these in combination with these couplers, we have discovered an alkylene dioxybenzene derivative that is specifically effective in preventing fading of color images and preventing discoloration of white backgrounds. An object of the present invention is to provide a method for improving the coloring efficiency of a coupler, reducing the amount of silver halide, and reducing the influence of PH fluctuations of a color developer on photographic properties. Another object of the present invention is to provide a method for reducing discoloration of a dye image and discoloration of a white background area after processing. The above-mentioned objects of the present invention are to provide a 4-(2-
This can be effectively achieved by containing at least one alkoxyarylthio)-5-pyrazolone coupler and at least one alkylenedioxybenzene derivative. That is, by using the magenta coupler and the alkylene dioxybenzene derivative in combination, the following surprising effects were obtained. Coupling of color developing agents (e.g., p-phenylenediamine type developing agents) with oxidation products has resulted in color images that are significantly more robust to light and heat. The degree of discoloration of the white background area due to light and heat after color development processing has been significantly reduced. The coloring efficiency of the magenta coupler was significantly improved. As a result, the amount of magenta coupler used can be reduced compared to conventional methods, and the amount of silver halide used can also be significantly reduced, which allows the coating thickness of the magenta color image-forming emulsion layer to be made thinner. I was able to do that. As a result, image sharpness was also significantly improved. By reducing the amount of coupler used and the amount of silver halide used, it was possible to produce color photographic materials at low production costs. The color development process became stable. (We obtained a photosensitive material that is extremely unaffected by PH changes in the photographic processing solution. Obtained a color photographic material with stable quality that does not develop abnormal colors even after being left in the presence of formalin before development. It was possible to obtain a color photographic material with excellent graininess in color images after development. The magenta coupler that leaves the arylthio group used in the present invention can be represented by the following general formula (). Yes. General formula () In the formula, Ar is at least one halogen atom,
represents an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a phenyl group substituted with a cyano group, R ₅ represents an alkyl group, an aryl group,
R ₆ is a hydrogen atom, a halogen atom, an acylamino group,
Represents a sulfonamide group, carbamoyl group, sulfamoyl group, alkylthio group, alkoxycarbonyl group, hydroxy group, alkyl group, alkoxy group or aryl group, m represents an integer from 1 to 4, and Y represents an acylamino group or anilino group. . Among the compounds represented by the general formula (), particularly preferred compounds can be represented by the general formula (). General formula () In the formula, R ₅ , m, and Ar have the same meanings as in the general formula (), X represents a halogen atom or an alkoxy group, and R ₆ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group. or represents an aryl group, R ₇ is a hydrogen atom,
Halogen atom, alkyl group, alkoxy group, acylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, diacylamino group, alkoxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, Arylthio group, alkyloxycarbonylamino group, alkylureido group, acyl group, nitro group,
Represents a carboxy group or trichloromethyl group. To explain Ar in more detail, Ar is a substituted phenyl group, and the substituents include halogen atoms (for example, chlorine atom, bromine atom, fluorine atom, etc.),
Alkyl group having 1 to 22 carbon atoms (e.g. methyl group, ethyl group, tetradecyl group, t-butyl group, etc.),
Alkoxy groups having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.), alkoxycarbonyl groups having 2 to 23 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxy group) carbonyl group, etc.) or a cyano group. To explain X in more detail, , etc.). To explain R ₇ in more detail, R ₇ is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom,
fluorine atom, etc.), linear or branched alkyl groups (e.g., methyl group, t-butyl group, tetradecyl group, etc.), alkoxy groups (e.g., methoxy group,
ethoxy group, 2-ethylhexyloxy group, tetradecyloxy group, etc.), acylamino group (e.g. acetamido group, benzamide group, butanamide group, tetradecaneamide group, α-(2,4-
di-tert-amylphenoxy)acetamide group,
α-(2,4-di-tert-amylphenoxy)butyramide group, α-(3-pentadecylphenoxy)hexanamide group, α-(4-hydroxy-
3-tert-butylphenoxy)tetradecanamide group, 2-oxo-pyrrolidin-1-yl group, 2
-oxo-5-tetradecylpyrrolidin-1-yl group, N-methyl-tetradecanamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octane sulfone group) amide group, p-dodecylbenzenesulfonamide group,
N-methyl-tetradecanesulfonamide group, etc.), sulfamoyl group (e.g., N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-[3-(dodecyloxy)-propyl])
Sulfamoyl group, N-[4-(2,4-di-tert
-amylphenoxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group (e.g., N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-[4-(2,4- di-tert-amylphenoxy)butyl]carbamoyl group, N-methyl-
N-tetradecylcarbamoyl group, etc.), diacylamino group (N-saccharinimide group, N-phthalimide group, 2,5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5-dioxo-1-
hydantoinyl group, 3-(N-acetyl-N-dodecylamino)succinimide group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g. , methoxysulfonyl group, octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), aryloxysulfonyl group (e.g., phenoxysulfonyl group, 2,4-
di-tert-amylphenoxysulfonyl group, etc.), alkanesulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, 2-ethylhexanesulfonyl group, hexadecanesulfonyl group, etc.), arylsulfonyl group (e.g. benzenesulfonyl group, etc.) group, 4-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g., ethylthio group, hexylthio group, benzylthio group, tetradecylthio group, 2-(2,4-di-tert-amylphenoxy)ethylthio group, etc.), Arylthio groups (e.g., phenylthio group, p-tolylthio group, etc.), alkyloxycarbonylamino groups (e.g., ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido groups ( For example, N-methylureido group, N,N-dimethylureido group, N-methyl-
N-dodecylureido group, N-hexadecylureido group, N,N-dioctadecylureido group, etc.), acyl group (for example, acetyl group, benzoyl group, octadecanoyl group, p-dodecaneamide benzoyl group, etc.) , represents a nitro group, a carboxy group or a trichloromethyl group. However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 38 carbon atoms. To explain R ₅ in more detail, R ₅ is an alkyl group having 1 to 22 carbon atoms (e.g., methyl group, propyl group, butyl group, 2-methoxyethyl group, methoxymethyl group, hexyl group, 2-ethylhexyl group, dodecyl group) group, hexadecyl group, 2-(2,4
-di-tert-amylphenoxy)ethyl group, 2-
dodecyloxyethyl group, etc.), and an aryl group (e.g., phenyl group, α- or β-naphthyl group, 4-tolyl group, etc.). R ₆ represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an aryl group having the same meaning as R ₇ above. Among the couplers represented by the general formula (),
Those in which the sum of the carbon numbers of R ₅ and R ₆ is 6 or more are particularly preferred in terms of achieving the object of the present invention. Typical coupler compounds of the present invention are shown below, but the present invention is not limited thereto. The coupler used in the present invention is a thiophenol derivative which is a corresponding coupling-off group and
-110943, it can be synthesized from a so-called 4-equivalent coupler in which the coupling active position is unsubstituted. The alkylene dioxybenzene compound used in the present invention can be represented by the following general formula (). General formula () In the formula, Z represents an alkylene group having 1 to 3 carbon atoms, substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a group represented by =S or a group represented by =O group. Good too. The number of substituents may be plural, and in this case, the plurality of substituents may be the same. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, acyl group,
Represents an acylamino group, a sulfonamide group, a diacylamino group, a carboxy group, a sulfo group, or a hydroxy group. Also, by R ₁ and R ₂ , R ₂ and R ₃

A group represented by the formula may be formed, or R ₁ and R ₂ or R ₂ and R ₃ may be ring-closed to form a 5- or 6-membered hydrocarbon ring or heterocycle. To explain in more detail the substituent of Z in general formula (), the substituent of Z is a hydrogen atom, a halogen atom, a straight chain, branched chain or cyclic alkyl group having 1 to 32 carbon atoms (for example, methyl, ethyl, isopropyl, t-butyl, n-octyl, t-octyl, dodecyl, cyclohexyl, hexadecyl, benzyl, etc.), aryl groups with 6 to 32 carbon atoms (e.g., phenyl, 1-naphthyl, etc.), 1 to 3 carbon atoms Up to 32 alkoxy groups (e.g.
Methoxy, ethoxy, n-octyloxy, t-
octyloxy, 2-ethylhexyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, benzyloxy, etc.) and aryloxy groups having from 6 to 32 carbon atoms (e.g. phenoxy, 1-naphthoxy, etc.) These alkyl groups, aryl groups, alkoxy groups, and aryloxy groups are selected from halogen atoms, nitro groups, cyano groups, thiocyano groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups,
Alkylcarbonyl group, arylcarbonyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, acyloxy group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, thioureido group, urethane group, thiourethane group, sulfonamide group,
Heterocyclic group, arylsulfonyloxy group, alkylsulfonyloxy group, arylsulfonyl group,
Alkylsulfonyl group, arylthio group, alkylthio group, alkylsulfinyl group, arylsulfinyl group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may be substituted with an N-arylanilino group, an N-acylanilino group, a hydroxy group, or a mercapto group. To explain R ₁ , R ₂ , R ₃ and R ₄ in general formula () in more detail, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a straight chain of carbon 1 to 32, or a branched chain. Chain or cyclic alkyl groups (e.g. methyl,
Ethyl, isopropyl, t-butyl, n-octyl, t-octyl, dodecyl, t-amyl, 1,
1-dimethyl-butyl, cyclohexyl, hexadecyl, cyclohexyl, benzyl, etc.), aryl groups having 6 to 32 carbon atoms (e.g. phenyl, 1-naphthyl, etc.), alkoxy groups having 1 to 32 carbon atoms (e.g. methoxy, ethoxy, n
-octyloxy, t-octyloxy, 2-ethylhexyloxy, dodecyloxy, hexadecyloxy, octadeoxy, benzyloxy,
), aryloxy groups having 6 to 32 carbon atoms (e.g., phenoxy, 1-naphthoxy, etc.),
Alkylthio group having 1 to 32 carbon atoms (e.g., methylthio, n-octylthio, n-dodecylthio, n-octadecylthio, etc.), 1 to 32 carbon atoms
up to 32 acyl groups (e.g. acetyl, octanoyl, tetradecanoyl, benzoyl, etc.),
Acylamino groups having 1 to 32 carbon atoms (e.g., acetamide, tetradecanamide, benzamide, etc.); sulfonamide groups having 1 to 32 carbon atoms (e.g., methanesulfonamide, ethanesulfonamide, benzenesulfonamide, etc.);
Diacylamino groups having 2 to 32 carbon atoms (e.g.
1-succinimide, 1-phthalimide, 1-hydantoinyl, 2,4-dioxo-3-oxazinyl, etc.), and these alkyl groups,
Aryl group, alkoxy group, aryloxy group,
Alkylthio group, acyl group, sulfonamide group,
Diacylamino groups include halogen atoms, nitro groups, cyano groups, thiocyano groups, aryl groups, alkoxy groups, aryloxy groups, carboxyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups,
Sulfo group, acyloxy group, sulfamoyl group,
Carbamoyl group, acylamino group, diacylamino group, ureido group, thioureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyloxy group, alkylsulfonyloxy group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylsulfinyl group, arylsulfinyl group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-
It may be substituted with an arylanilino group, an N-acylanilino group, a hydroxy group, or a mercapto group. Further, R ₁ , R ₂ , R ₃ and R ₄ represent a carboxyl group, a sulfo group, or a hydroxy group. Hydrocarbon rings formed by ring closure of R ₁ and R ₂ and R ₂ and R ₃ include indane rings, spiroindane rings, naphthalene rings, tetrahydronaphthalene rings, etc., and these include halogen atoms, nitro groups,
Cyano group, thiocyano group, alkyl group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, acyloxy group, sulfamoyl group, carbamoyl group , acylamino group, diacylamino group, ureido group, thioureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, tharylsulfonyloxy group, alkylsulfonyloxy group, arylsulfonyl group, alkylsulfonyl group, arylthio group, Alkylthio group, alkylsulfinyl group,
It may be substituted with an arylsulfinyl group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group or mercapto group. Also, in the spiroindane ring

The group represented by [Formula] is substituted A bone core like this may be formed. Heterocycles formed by ring closure of R ₁ and R ₂ and R ₂ and R ₃ include chroman ring, coumaran ring, spirocoumaran ring, spirochroman ring, etc. These are halogen atoms, nitro groups, cyano groups, thiocyanos group, alkyl group, aryl group, alkoxy group,
Aryloxy group, carboxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, acyloxy group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, thioureido group, urethane basis,
Thiourethane group, sulfonamide group, heterocyclic group,
Arylsulfonyloxy group, alkylsulfonyloxy group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
Substituted with alkylsulfinyl group, arylsulfinyl group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group and mercapto group You can leave it there. In addition, spirochroman rings and spirocoumaran rings have

The group represented by [Formula] is substituted The bone nucleus represented by or A bone core represented by may be formed. Among the compounds represented by the general formula (), Z is preferably unsubstituted alkylene or an alkylene group substituted with an alkyl group or an aryl group. _R1 ,
R ₂ , R ₃ , and R ₄ are hydrogen atoms, halogen atoms,
An alkyl group, an alkoxy group, and an alkylthio group are preferable, and the ring-closing position between R ₁ and R ₂ and R ₂ and R ₃ is preferably the ring-closing position between R ₂ and R ₃ . R ₂ and R ₃

It is also preferable that it forms a group represented by the formula: As the compound group in which R ₂ and R ₃ are ring-closed, a chroman ring and a spirochroman ring are preferable. The color image stabilizer of the general formula () used in the present invention is a 4-
(2-alkoxyarylthio)-5-pyrazolone coupler, usually 0.5 to 200% by weight,
Preferably, it is used in a range of 2 to 150 weight percent. Further, the compound represented by the general formula () is a known antifading agent such as a hydroquinone derivative, a hydroxychroman derivative, a hydroxyspirochroman derivative, or a derivative in which the hydroxyl group of a hydroquinone derivative, a hydroxychroman derivative, a hydroxyspirochroman derivative is changed to an alkoxy group, or The effect is even greater when used in combination with an alkoxyphenol derivative. Next, examples of alkylene dioxybenzene derivatives used in the present invention will be shown, but the invention is not limited thereto. The alkylene dioxybenzene derivative used in the present invention can be obtained by reacting an ortho-dihydroxybenzene derivative with an alkylene dihalide.
The method described in No. 56-52747 was used. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), Photographic by GFDuffin
Emulsion Chemistry (published by The Focal Press)
(1966), Making and VL Zelikman et al.
Coating Photographic Emulsion (The Focal
Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a combination thereof, or the like. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. The coupler and antifading agent used in the present invention can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azetate), trimesic acid esters (e.g. tributyl trimesate) or organic solvents with a boiling point of about 30°C to 150°C, such as low alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. After being dissolved in a hydrophilic colloid, it is dispersed in a hydrophilic colloid.
The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. Example 1 Magenta coupler-1-(2,4,6-trichlorophenyl)-3-{(2-chloro-5-tetradecanamido)anilino}-4-{(2-n-butoxy-5-t- 10 g of octyl)phenylthio}-2-pyrazolin-5-one (coupler 5), 20 ml of tricresyl phosphate, and 20 ml of ethyl acetate.
Dissolve this solution in a gelatin solution containing 8 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 100g. Next, this emulsified dispersion was mixed with 120 g (containing 7 g of Ag) of a green-sensitive silver chlorobromide emulsion (Br 50 mol%), sodium dodecylbenzenesulfonate was added as a coating aid, and the mixture was placed on a paper support laminated on both sides with polyethylene. It was applied to. The coupler application amount was set at 300 mg/m ² . Sample A was prepared by applying a gelatin protective layer (gelatin 1 g/m ² ) on this layer. When preparing the above emulsified dispersions in the same manner, the compounds of the present invention and comparative compounds were added as shown in the table, and other than that, samples B to M were prepared in the same manner as sample A. These samples were exposed to light at 1000 lux for 1 second and treated with the following processing solution. Developer Benzyl alcohol 15ml Diethylenetriaminepentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxyamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-β-
(methanesulfonamide)ethylaniline, 3/2
H ₂ SO ₂・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Make up to 1000ml with water PH6. 8 Processing process Temperature Time Developer 33° 3 minutes 30 seconds Bleach-fix solution 33° 1 minute 30 seconds Water Washing 28-35° 3 minutes For each sample with a dye image formed in this way
A xenon tester (illuminance 20
A fading test was conducted for 5 days using a 5-day test tube. The measurement was carried out using a Macbeth Densitometer RD-514 model (Status AA filter), and the density change in the 2.0 density part of the initial density and the density change in the white background part were measured.

【table】

【table】

[Table] Example 2 Using the same compound as the magenta coupler (Example 1), a coating composition for the third layer of the table composition was prepared according to the method of Sample A of Example 1, and a table containing the third layer was prepared. Multilayer samples (Samples P to R) were prepared. These samples were exposed and processed in the same manner as in Example 1, and each sample with a dye image formed thereon was subjected to a fading test for 4 weeks using a fluorescent lamp bleacher (20,000 lux). The results are shown in the table.

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. Contains at least one 4-(2-alkoxyarylthio)-5-pyrazolone type magenta dye-forming coupler and at least one compound represented by the following general formula (). Silver halide color photographic material with general formula () In the formula, Z represents an alkylene group having 1 to 3 carbon atoms, substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a group represented by =S or a group represented by =O. Good too. The number of substituents may be plural, and in this case, the plurality of substituents may be the same. R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, acyl group, acylamino group, sulfonamide group, diacylamino group, carboxy represents a group, a sulfo group, or a hydroxy group. Furthermore, R ₁ and R ₂ or R ₂ and R ₃ may form a group represented by the formula, and R ₁ and R ₂ or R ₂ and R ₃ may be ring-closed to form a 5- or 6-membered group. A heterocycle selected from a hydrocarbon ring or a chroman ring, a claman ring, a spirocoumaran ring or a spirochroman ring may be formed.