JPH0414336B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic light-sensitive material, and more particularly to a novel two-equivalent magenta coupler, and more particularly to a silver halide color photographic light-sensitive material having good color development and excellent storage stability. Hitherto, a two-equivalent magenta coupler has been known in which a substituent is introduced into the active site of the magenta coupler to improve silver utilization efficiency. These two-equivalent magenta couplers include, for example, halogen-substituted types (US Pat. No. 3,006,579, etc.), aryloxy-substituted types (US Pat. No. 3,419,391, etc.), and carbonyloxy-substituted types (US Pat. Nos. 3,311,476 and 3,422,521). , Japanese Patent Publication No. 1973-
129535, etc.), nitrogen or sulfur substitution type (Japanese Patent Application Laid-Open No. 1973
-53372, 50-122935, etc.), carbon-substituted type (US Patent No. 2632702, JP-A-51-37646, etc.), substituted methylene-substituted type (British Patent No. 963461, JP-A No. 51-37646, etc.),
34-4036, etc.), methylene. Alkylidene or arylidene bis type (US Patent No. 2,618,641, British Patent No. 736,859, British Patent No. 968,461, Japanese Patent Publication No. 1973-
No. 16110, No. 44-26589, No. 49-37854, JP-A-49-29638, etc.). Although these two-equivalent type magenta couplers have characteristics such as a faster dye formation rate and a higher maximum color density than four-equivalent type magenta couplers, they are not necessarily satisfactory. In particular, the above-mentioned U.S. Pat.
The couplers described in No. 3311476, No. 3432521, JP-A-49-129535, etc. have the disadvantage of being unstable because they are active themselves. Therefore, there have been problems in that fogging is likely to occur during color development, yellow staining is likely to occur in uncolored areas or low density areas, and color development deteriorates over time. Further, as previously disclosed in US Pat. No. 3,227,554, couplers in which the active site of the coupler is substituted with an alkylthio group, an arylthio group, or a heterocyclic thio group are known. but,
These couplers are inhibitor releasable couplers (DIR
The arylthio group, heterocyclic thio group, or alkylthio group released from the coupling active site of the coupler during the development process has the function of delaying the development of silver halide. On the other hand, recently, JP-A-55-135835
As disclosed in No. 1, the active site of the coupler is substituted with a heterocyclic thio group, and a hydrophilic group is introduced into the heterocyclic group directly or through a phenylene group.
A DIR coupler is known, and this coupler has the same function as the above-mentioned DIR coupler. On the other hand, the magenta coupler according to the present invention has a heterocyclic thio group substituted at the active site of the magenta coupler as shown in the following general formula [], and further substituents (-J)-nX-Y However, it does not have the function of a DIR coupler, and has significantly improved color development and is 2-equivalent (however,
Here, 2-equivalent means that when added in the same molar amount as a 4-equivalent coupler, it has a color forming property greater than that of a 4-equivalent coupler. This effect was not observed in yellow couplers or cyan couplers. Therefore, a first object of the present invention is to provide a novel two-equivalent magenta coupler whose active site is substituted with a group capable of coupling off with the oxidation product of an aromatic amine developing agent. . A second object is to provide a novel two-equivalent magenta coupler that has high color development and forms dye images without unnecessary fog or stain. The third object is to provide a color photographic material in which the magenta coupler is not inactivated by formalin gas or aging. The fourth object is to provide a color photographic light-sensitive material in which silver halide in a photographic emulsion layer containing the novel 2-equivalent magenta coupler is reduced and the sharpness of the obtained color image is improved by using the novel 2-equivalent magenta coupler. It is. The fifth object is to provide a color photographic material in which a color image formed by the novel two-equivalent magenta coupler has excellent fastness. Other objects of the invention will be further understood from the following detailed description and examples. The object of the present invention has been achieved by a silver halide color photographic material characterized by containing a magenta coupler represented by the following general formula. general formula In the formula, R ₁ represents an alkyl group, an aryl group, or a heterocyclic group, R ₂ represents an amino group, a carbonamide group, a ureido group, an alkoxy group, or a heterocyclic group, and Z represents a 5- or 6-membered heterocyclic group. (including fused heterocycles), n represents 0 or 1, X represents an alkylene group, and when n is 1, X represents an alkylene group, an arylene group, or a heterocycle. represents a group, Y is -COOM group,
-OM group (M represents a hydrogen atom, ammonium ion or alkali metal ion). To explain the coupler of the present invention in more detail, the alkyl group for R ₁ in the general formula includes an alkyl group having 1 to 22 carbon atoms [for example, a methyl group, an ethyl group, a t-butyl group, an octyl group, a dodecyl group, Halogen-substituted alkyl groups (e.g., 2-chlorobutyl group, ω-bromooctyl group, etc.), hydroxy-substituted alkyl groups (e.g., 3-hydroxyheptyl group, ω-hydroxydecyl group, etc.), and phenyl-substituted alkyl groups (e.g., 2-hydroxyheptyl group, ω-hydroxydecyl group, etc.) Phenylpropyl group, (2,4,6-trichlorophenyl)
Ethyl group etc. ] is desirable. The aryl group for R ₁ is preferably a phenyl group, specifically a phenyl group, a halogen-substituted phenyl group (for example, 2,
4,6-trichlorophenyl group, 2,4,6-trifluorophenyl group, etc.) halogen- and alkoxy-substituted phenyl groups (e.g., 2,4-dichloro-4-methoxyphenyl group, etc.) and halogen atoms, alkylcarbonyl A phenyl group substituted with an oxy group, an arylcarbonyloxy group, an acylamido group, an alkyl group, an alkoxy group, etc. (e.g., 2,6-dichloro-4-dodecanamidophenyl group, 2,6-dichloro-4-tetradecyl group) Oxycarbonylphenyl group, 2-methoxy-4
-propyloxycarbonylphenyl group, 4-
(2,4-di-t-amylphenoxy)acetamidophenyl group, 4-tetradecanamide group, etc.)
etc. is desirable. Furthermore, the heterocyclic group of R ₁ may be substituted, and for example, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, pyrrolidinyl group, piperidinal group, etc. are preferable, and more specifically, benzothiazolyl group, 6 -Chlorobenzothiazolyl group, benzoxazolyl group, 5-pentanamidobenzoxazolyl group, 6-methoxybenzimidazolyl group, etc. are desirable. In the general formula, the amino group for _R2 is an amino group, an alkyl-substituted amino group (e.g., methylamino group, dodecylamino group, N-ethyl-N-
hexylamino group, etc.) and phenyl-substituted amino groups (e.g., phenylamino group, 2-chloro-5
-tetradecanamidephenylamino group, 2-trifluoromethyl-5-tetradecylcarbamoylamino group, 2,4-dichlorophenylamino group, N,N-diphenylamino group, N-ethyl-
N-tolylamino group, etc.) are desirable. Furthermore, carbonamide groups include alkylcarbonamide groups (e.g., ethylcarbonamide group, dodecylcarbonamide group, phenylethylcarbonamide group, etc.) and arylcarbonamide groups (e.g., phenylcarbonamide group, 2,4,6 -trichlorophenylcarbonamide group, 3-[α-
(2,4-di-tert-amylphenoxy)acetamido]benzamide group, etc.) are desirable. Furthermore, the ureido group includes alkylureido groups (e.g., hexylureido group, tetradecylureido group, benzylureido group, etc.) and arylureido groups (e.g., phenylureido group, 3-pentadecylureido group, N-dodecyl-N-phenylureido group). etc.) is desirable. Furthermore, as the alkoxy group, for example, a methoxy group, an ethoxy group, a t-butoxy group, etc. are preferable. The heterocyclic group has the same meaning as the heterocyclic group for _R1 , and is preferably, for example, a pyrrolidinyl group or a piperidinyl group. Examples of the 5- or 6-membered heterocyclic group formed by z include a tetrazolyl group (e.g., 1-methyltetrazolyl group, etc.), a thiadiazolyl group (e.g., 1,3,4-thiadiazolyl group, etc.), and an oxadiazolyl group. (for example, 1,3,4-oxadiazolyl group, etc.), thiazolyl group (for example, benzthiazolyl group, etc.), oxazolyl group (for example, benzoxazolyl group, etc.), imidazolyl group (for example, benzimidazolyl group, etc.), triazolyl group ( Examples include 4-phenyl-1,2,4-triazolyl group, birimidyl group, and the like. These heterocyclic groups include those substituted with amino groups, alkyl groups, cycloalkyl groups, aryl groups, acyl groups, etc. at appropriate positions. In the formula, the alkylene group represented by X is
Alkylene groups having 1 to 12 carbon atoms (for example, methylene group, ethylene group, isobutylene group, cyclobenzenylene group, cyclohexylene group, benzylene group, phenylethylene group, arylene group, cyclohexenylene group, etc.), etc. These are halogen atoms,
It may be substituted with a nitro group, cyano group, aryl group, alkoxy group, amino group, aryloxy group, acyloxy group, or a group represented by Y in the general formula. In the general formula, preferred groups represented by (-S)-nX-Y are described below. Next, typical examples of the magenta coupler of the present invention will be given, but the magenta coupler of the present invention is not limited thereto. The above two-equivalent magenta coupler according to the present invention is
It can be synthesized by the following method. Synthesis Example 1 (Synthesis of Exemplary Compound-3) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecenylsuccinimide)anilino-5-pyrazolone 3.6g (4.9×10 ^-3
mol) and 0.87 g (4.9 x 10 ^-3 mol) of 1-carboxymethyl-5-mercaptotetrazole were dissolved in 25 ml of dimethylformamide and stirred. A solution of 0.78 g (4.9 x 10 ^-3 mol) of bromine diluted in 5 ml of dimethylformamide was added dropwise to this solution over a period of about 30 minutes at room temperature. After the dropwise addition, the reaction was allowed to take place for about 1 hr. Then, the reaction solution was poured into water and 200 ml of ethyl acetate was added. Add and extract. After washing with water, drying with anhydrous sodium sulfate,
After distilling off the solvent, column purification is performed. 2.8 g of Exemplified Compound-3 in the form of a column was obtained. Synthesis Example 2 (Synthesis of Exemplified Compound-6) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecenylsuccinimide-anilino-5-pyrazolone 3.6g (4.9×10 ^-3
mol) and 1.08 g of 2-carboxyethylthio-5-mercapto-1,3,4-thiadiazole
(4.9×10 ^-3 mol) was dissolved in 25 ml of dimethylformamide, and while stirring, 0.78 g of bromine (4.9×
A solution prepared by diluting 10 ^-3 mol) in 5 ml of dimethylformamide was added dropwise at room temperature over about 30 minutes.
Allowed time to react. Pour the reaction solution into water and add ethyl acetate.
Add 300ml and extract. After washing with water, drying with anhydrous sodium sulfate, distilling off the solvent, and performing column purification to obtain 3.0 g of Exemplified Compound-6 in column form.
I got it. The magenta coupler according to the present invention produced by the above synthesis method is used for photographic purposes in order to form excellent images, but its usage is by dissolving it in an aqueous alkaline solution and adding it to a silver halide emulsion layer. High boiling point solvents such as dioctyl butyl phosphate, tributyl phosphate, tricresyl phosphate, dibutyl phthalate, diethyl laurylamide, 1,4-dicyclohexylmethyl-2-ethyl-hexanoate and/or Alternatively, it can be dissolved and dispersed using ethyl acetate and added to the silver halide emulsion layer, or methanol, acetone,
It can also be used by dissolving it in a low boiling point solvent such as tetrahydrofuran and adding it to the silver halide emulsion layer. When added to the constituent layers of the above photosensitive material,
Although it may be added to any of the constituent layers, it is preferably added to the edge-sensitive emulsion layer, and the amount added in this case is 0.001 to 1 mole of silver halide contained in the emulsion. 3.0 mol, preferably
It is 0.01-1.0 mol. The above silver halide used in the present invention is any silver halide such as silver chloride, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. can be produced by various methods such as a neutral method and an ammonia method depending on the type of photosensitive material. These silver halides include active gelatin, sulfur sensitizers (e.g. allylthiocarbamide, thiourea, cystine, etc.), selenium sensitizers, reduction sensitizers (e.g. stannous salts, polyamines, etc.), and noble metal sensitizers. (e.g. gold, ruthenium, rhodium,
It is chemically sensitized by using a water-soluble salt such as indium (water-soluble salt such as indium) alone or in combination as appropriate. Furthermore, this silver halide can be optically sensitized to a desired wavelength range, such as a zeromethine dye,
Optical sensitization can be carried out using dianine dyes such as monomethine dyes, dimethine dyes, and trimethine dyes, or optical sensitizers such as merocyanine dyes, alone or in combination. As the support for the photosensitive material, known film or sheet materials such as paper, laminated paper, glass, cellulose acetate, polyester, and polycarbonate can be used. The photographic light-sensitive material to which the coupler of the present invention is added is composed of at least a support and a photosensitive layer provided thereon, but as described above, various layer structures can be adopted depending on the purpose. Generally, it is composed of several layers or more. The magenta coupler according to the present invention can be used in appropriate combinations thereof, and can also be used in combination with other 2-equivalent couplers, 4-equivalent couplers, colored couplers, etc.
Couplers having different hues of color-forming dyes are contained in the photosensitive layer for an appropriate photosensitive wavelength range. That is, when producing the multilayer color light-sensitive material according to the present invention, as couplers having different hues of coloring dyes, for example, benzoylacetanilide-based and pivaloylacetanilide-based yellow couplers, phenol-based and naphthol-based cyan couplers, etc. are used. DIR couplers, colored couplers, or other types of magenta couplers are selected and used as necessary. Regarding these couplers, for example, JP-A-48-29432, JP-A-48-66834,
No. 50-112038, No. 53-52423, No. 53-109630
No. 54-133329, No. 54-145135, Special Publication No. 1973
-37854, US Pat. No. 3,684,514, etc., and may also be selected from compounds described in Research Disclosure (RD) 19633, RD19536, etc. Furthermore, the photographic light-sensitive material according to the present invention may contain various photographic additives in the light-sensitive layer and/or other constituent layers (for example, intermediate layer, subbing layer, filter layer, protective layer, image-receiving layer, etc.) depending on the purpose. Such photographic additives may include, for example, stabilizers,
Sensitizers, film property improvers, hardeners, spreading agents, coupler solvents, and so-called compounds that release development inhibitors during color development and produce substantially colorless compounds.
There are DIR compounds, antistatic agents, antifoaming agents, ultraviolet absorbers, optical brighteners, anti-slip agents, matting agents, antihalation agents, and anti-irradiation agents.These various photographic additives include: Each may be used alone or in combination. On the other hand, the color developing solution for color developing the photosensitive material after exposure has a color developing agent as a main component as described above, but the color developing agent used in the present invention is an aromatic primary amine, and in particular, A typical example is p-phenylenediamine. After color development processing, when silver halide or developed silver in a light-sensitive material is removed from the system, a bleach-fix solution is generally used, but the fixing component is a halogenated solution such as sodium thiosulfate or ammonium thiosulfate. A silver solvent is used, and the bleaching ingredients are red blood salt, ethylenediaminetetra, and diacetic acid.
Iron ammonium or sodium salt is used. Further, the photosensitive material containing the coupler according to the present invention can also be processed with an alkaline processing solution called a so-called alkaline activator. Silver halide color photographic light-sensitive materials containing the coupler of the present invention include, for example, silver halide light-sensitive materials for diffusion transfer systems, negative light-sensitive materials for general use, reversal light-sensitive materials for general use, positive light-sensitive materials for general use, and direct positive light-sensitive materials. It is used as such. In addition to the above, the magenta coupler of the present invention can also be applied to light-sensitive materials subjected to an amplifier treatment using a cobalt () complex, hydrogen peroxide, etc., with an extremely reduced amount of conventional silver halide used. As explained in detail above, the magenta coupler of the present invention having the structure represented by the above general formula has excellent photographic properties such as sensitivity, maximum density, fogging, and yellow staining, and also has improved storage stability.
In particular, it can be effectively and widely used in silver-saving color photography technology. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 1 x 10 ^-2 mol of exemplified coupler (3) was heated and dissolved in a mixture of 15 ml of dibutyl phthalate and 30 ml of ethyl acetate, and this solution was dissolved in a 5% solution containing 1.5 g of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont). It was mixed with 300 ml of gelatin aqueous solution and emulsified and dispersed using a colloid mill. A dispersion of this coupler was mixed with 200 g of a photographic emulsion containing 5 x 10 ^-2 mol of green-sensitive silver chlorobromide (20 mol% silver chloride, 80 mol% silver bromide) and 10 g gelatin. 10 ml of a 2% solution of 2-bis(vinylsulfonyl)ethane was added, coated on a polyethylene-coated paper support and dried. A protective gelatin layer is applied on top of this layer to create a color photographic material sample.
(1) was created. At this time, the amount of silver coated on sample (1) is
It was 0.5g/ ^m2 . Additionally, instead of example coupler (3), example coupler
Samples (2) and (3) were prepared using (4) and (6) in exactly the same manner as above. For comparison, samples (4) to (8) was created. In addition, as a comparative coupler, a compound having the following structure was used. After each of these samples (1) to (8) was wedge exposed in a conventional manner, they were subjected to the following processing steps and processed using a developer having the following processing solution composition. [Processing process (33℃)] Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 3 minutes [Color developer composition] 4-Amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 4.0g Benzyl alcohol 10.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Potassium bromide 0.2g Anhydrous sodium sulfite 2.0g Diethylene glycol 3.0ml Add water to adjust the pH to 1 and adjust the pH to 10. Adjust to 0. [Bleach-fix solution composition] Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 10.0g Sodium metabisulfite 3.0g Add water to 1 and adjust to pH 6.6. The obtained magenta dye image was measured using a densitometer (PD-7R).
Measured with green light using Konishiroku Photo Industry Co., Ltd.)
The color development sensitivity, fog and maximum density were calculated and the results are shown in Table 1.

[Table] The sensitivity is expressed as a relative sensitivity when the sensitivity of Sample 4 is set to 100. Samples (1) to (3) using couplers of the present invention have higher sensitivity and Dmax than samples (4), (5), and (8) using comparative couplers.
It can be seen that the image quality is good, with high co-existence and little fog. In addition, the samples using the comparative couplers (C) and (D) have inferior coloring properties than the comparative 4-equivalent couplers, but the samples using the couplers of the present invention have good coloring properties, which indicates the usefulness of the present invention. is understood. Immediately after coating, the coated samples (1) to (8) prepared above were exposed and developed in the same manner as described above. On the other hand, after coating the above coating sample, it was stored unexposed under natural conditions (25°C, 60% relative humidity) for 3 months, and then exposed and developed in the same manner as above to examine the decrease in magenta color density over time. Ta. The results are shown in Table 2. The values in the table indicate the maximum magenta color density produced by the green filter.

【table】

[Processing process (38℃)]

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds [Color developer composition] 4-Amino-3-methyl- N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and adjust the pH to 10.0 using potassium hydroxide. [Bleach solution composition] Ethylenediaminetetraacetic acid ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide 150.0g glacial acetic acid 10.0ml Add water to make 1 and use ammonia water
Adjust to pH6.0. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162 ml Anhydrous sodium sulfite 12.4 g Add water to make 1, and adjust to pH 6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The magenta dye image obtained above was measured with green light using a densitometer (pD-7R Konishiroku Photo Industry Co., Ltd.), and the color development sensitivity (relative sensitivity when the sensitivity of sample (12) was set as 100) (expressed as a value), fog and maximum sensitivity were calculated, and the results are shown in Table 3.

[Table] From Table 3, samples (9) using the coupler of the present invention
～(11) is sample (12) using comparative coupler～
(14) It can be seen that the sensitivity and Dmax are clearly higher, and the fog is less and shows good results. On the other hand, samples (9), (10), (11),
After coating (12), (13) and (14), the samples were left unexposed in a sealed container containing a 1% formaldehyde aqueous solution in a dark room for 3 days without contact with the solution. These samples and untreated samples for comparison were exposed and developed in the same manner as in Example-2, sensitivity and maximum density were measured, and formalin resistance % (treated sample/untreated sample x 100) was calculated. The results obtained are shown in Table 4.

[Table] From Table 4, samples using the coupler of the present invention
(9), (10), and (11) are less susceptible to adverse effects such as decreased sensitivity and maximum concentration due to formalin gas than samples (12), (13), and (14) using comparative couplers, and have better shelf life for raw samples. It can be seen that this is a coupler with excellent properties. Example 3 High-sensitivity color negative photosensitive material (15) with the following layer structure on a transparent triacetate film support
and (16) were created. 1st layer Anti-halation layer Gelatin layer containing black colloidal silver (dry film thickness
1μ) 2nd layer Intermediate layer Gelatin layer containing 2,5-di-t-octylhydroquinone (dry film thickness 1μ) 3rd layer Red-sensitive emulsion layer 1-hydroxy-4-[(3-methoxypropyl)amino as a coupler carbonylmethoxy]-
N-[4-(2,4-di-t-pentylphenoxy)butyl]-2-naphthamide at 6.8×10 ^-2 mol per mol of silver halide, 1-hydroxy-N-{δ as a colored coupler -(2,4-di-t
-amylphenoxy)butyl}-4-(2-ethoxycarbonylphenylazo)-2-naphthamide at 1.7×10 ^-2 mol, and 2-(1-phenyl-5-tetrazolylthio)-4 as a development inhibitor-releasing substance.
-(2,4-di-t-amylphenoxyacetamide)-1-indanone was weighed out in 4 x 10 ^-3 mol,
Dissolve tricresyl phosphate and ethyl acetate, emulsify and disperse in the same manner as in Example 1, and add the resulting dispersion to a red-sensitive silver iodobromide emulsion (8 mol% silver iodide, Add to 500 g of silver oxide (92 mol%),
Coated and dried. (Coated silver amount 2.0g/m ² , dry film thickness
6μ) 4th layer Intermediate layer 5th layer same as the 2nd layer Edge-sensitive emulsion layer Exemplary coupler (10) at 5.8% per mole of silver halide
×10 ^-2 mol and 1-(2,
1.7 x 10 ^-2 mol of 4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimide)anilino-4-(4-hydroxyphenylazo)-5-pyrazolone and development. Inhibitor substance (DIR
2-(1-phenyl-5-tetrazolylthio)-4-(octadecylsuccinimide)
Weighed 2 x 10 ^-3 moles of -1-indanone, prepared an emulsified dispersion using tricresyl phosphate and ethyl acetate, and prepared a green-sensitive silver iodobromide emulsion (silver iodide 6
silver bromide (94 mol%) was added to 500 g of silver bromide, coated and dried. (Coated silver amount 2.0g/m ² , dry film thickness 6μ) 6th layer Intermediate layer 7th layer same as 2nd layer Yellow filter layer Gelatin layer containing yellow colloidal silver and 2,5-di-t-octylhydroquinone ( (dry film thickness 1μ) 8th layer Blue-sensitive emulsion layer α-pivaloyl-α-(3,5-dioxo-1,2-diphenyl-triazolidin-4-yl)-2-chloro- per mole of silver halide as a coupler 5-{γ-(2,4-di-t-amylphenoxy)butyramide-acetanilide 2.5×
10 to ₁₂ mol was emulsified and dispersed using tricresyl phosphate and ethyl acetate, added to 500 g of blue-sensitive silver iodobromide emulsion (7 mol % silver iodide, 93 % silver bromide), and coated. (Coated silver amount 1.2g/m ² , dry film thickness 5μ) 9th layer Protective layer Add 400ml of 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane using gelatin as a hardening agent.
The dry film thickness was 1μ. The thus obtained sample (15) was coated in the same manner as sample (15) except that the exemplary coupler (10) in the fifth layer was replaced with comparative couplers (F) and (C).
(17) was created. Table 5 shows the photographic performance results of the samples thus obtained, which were wedge exposed through a green filter and developed in the same manner as in Example 2. (The sensitivity is expressed as a relative sensitivity value when sample (16) is taken as 100.)

[Table] From Table 5, it is understood that the coupler of the present invention is a multilayer color negative sample and has high sensitivity and good gradation. Example 4 A color paper material having the following layer structure was prepared on a polyethylene resin-coated support. 1st layer Blue sensitive layer α-pivaloyl-α (2,
4-Dioxo-1-benzylimidazodine-3-
yl)-2-chloro-5-[γ-(2,4-di-t
-Amylphenoxy)butyramide]-acetanilide (1.5 x 10 ^-2 mol) was weighed and dispersed in a usual emulsion using dibutyl phthalate to form a blue-sensitive silver chlorobromide emulsion (silver bromide 20 mol%, silver chloride 80 mol%) 5x ^10-2
The mixture was mixed with 200 g of a photographic emulsion containing 10 g of gelatin and coated. (Amount of coated silver 400 mg/m ² ) Second layer Intermediate layer Gelatin layer containing 2,5-di-t-octylhydroquinone Third layer Green-sensitive layer Exemplary coupler (6) was mixed with 1×10 _-2 mol and 2, 5-G-
5 x 10 ^-4 mol of t-octylhydroquinone and 1,4-di-octyloxy- as a photofading inhibitor.
Weighed 3 x 10 ^-3 moles of 2,5-di-t-amylbenzene, emulsified and dispersed it in a conventional manner using dibutyl phthalate, and prepared a green-sensitive silver chlorobromide emulsion (80 mol% silver bromide, silver chloride). 20 mol%) 5×10 ^-2 mol and gelatin
It was mixed with 200 g of photographic emulsion containing 10 g and coated. (Coated silver amount: 500 mg/dm ² ) 4th layer Intermediate layer: 2,5-di-t-octylhydroquinone and 2-(benztriazole-2) as an ultraviolet absorber.
-yl)-4,6-di-t-butylphenol and 2-(benztriazol-2-yl)-4-t-
It was coated containing butylphenol. (Coating film thickness 2 μ) 5th layer Red-sensitive layer 2-[α-(2,4-di-
t-Amylphenoxy)-butyramide]-4,6
-di-chloro-5-methyl phenol 1.5x
Weigh 10 ^-2 mol, emulsify and disperse it in the usual manner with dibutyl phthalate, and add 5 x 10 ^-2 mol of red-sensitive silver chlorobromide emulsion (80 mol% silver bromide, 20 mol% silver chloride) and 10 mol of gelatin.
The mixture was mixed with 200 g of photographic emulsion containing g and coated. (Coated silver amount 400mg/m ² ) 6th layer Protective layer 1,2 as a hardening agent to the protective layer made of gelatin
- 200 ml of a 2% aqueous solution of bis(vinylsulfonyl)ethane was added and applied. (Film thickness: 1μ) The sample prepared in this manner was designated as (18). Furthermore, the example coupler (6) of the third layer is compared with the coupler
Sample (19) was prepared in exactly the same manner as above except for changing to (C). The samples (18) and (19) obtained in this way were passed through a green filter.
Table 6 shows the results of developing and examining photographic performance in the same manner as in Example 1. Note that the sensitivity is expressed as a relative sensitivity when sample (19) is taken as 100.

[Table] From Table 6, it was understood that the couplers of the present invention had clearly better coloring properties than the comparative couplers. On the other hand, the above color developer samples (18) and (19) were placed in a xenon fade meter for one week to examine light resistance and yellow stain in uncolored areas. In addition, to examine the heat resistance of the dye, it was dried at 77°C for two weeks. In addition, to examine the moisture resistance of the dye, treatment was performed at 60°C and 80% RH for two weeks. In addition, for the dye residual rate of each treatment, the initial density of untreated is D=
The results are shown in Table 7, expressed as residual percentage at 1.0.
In addition, the density of yellow stain was measured through a blue filter.

[Table] From Table 7, it can be seen that sample (18) of the present invention has better dye storage stability and staining in uncolored areas than the comparative couplers.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic material characterized by containing a magenta coupler represented by the following general formula. general formula [In the formula, R ₁ represents an alkyl group, an aryl group, or a heterocyclic group, R ₂ represents an amino group, a carbonamide group, a ureido group, an alkoxy group, or a heterocyclic group, and Z represents a 5- or 6-membered heterocyclic group. (including fused heterocycles), n represents 0 or 1, X represents an alkylene group, Y represents a -COOM group, -OM group (M is a hydrogen atom, an ammonium ion or represents an alkali metal ion.), represents].