JPH0566574B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler that forms magenta dye images with high color development and improved storage stability, especially light fastness. More specifically, the present invention relates to a silver halide color photographic light-sensitive material containing a novel 1H-pyrazolo[3,2-c]-S-triazole magenta coupler.

[Prior art]

In general, in silver halide color photographic materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and the oxidized products of the color developing agent produced at this time are combined with yellow, magenta and A dye image can be obtained by coupling with a coupler forming each cyan dye. Pyrazolone couplers have been used in practical use to form the magenta dye, but these have unfavorable side absorption and are said to have poor storage stability, especially resistance to formalin gas (formalin resistance). It has its drawbacks. In order to improve the above drawbacks, various 1H
-Pyrazolo[3,2-c]-S-triazole magenta couplers have been proposed. For example, US Patent No. 3725067, British Patent No. 1252418, British Patent No. 1334515
listed in the number. The compounds described in both patents are of course superior to pyrazolone magenta couplers in terms of side absorption, but improvements in formalin resistance are insufficient, and little improvement has been shown in terms of color development and image light resistance. . Research
The compound described in Disclosure 12443 is also of no practical use in terms of color development. The 1H-pyrazolo[3,2-c]-S-triazole type magenta coupler described in JP-A No. 58-42045 has been significantly improved in terms of formalin resistance and color development, but it still has improved light resistance. has hardly been done. Also, the couplers described in JP-A-59-99437 and JP-A-59-125732 have improved color development, but
There continues to be no improvement in the lightfastness of dye images based on the described couplers. In the latter case, the light resistance of the image is simply improved by the additive used in combination. However, although the former coupler of Compound Example 19 described in the specification has slightly improved light resistance, it cannot be said to be sufficient. In other words, even though 1H-pyrazolo[3,2-c]-S-triazole magenta couplers have attracted attention for their lack of side absorption and high formalin resistance, little improvement has been made in terms of the light resistance of dye images. I can say no.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material that has good light resistance and formalin resistance and high color development.

[Structure of the invention]

The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion contains a secondary alkyl at the 3rd position and a secondary alkyl at the 6th position. Alkyl, the 7th position is substituted with a leaving group other than a hydrogen atom
This is achieved by a silver halide color photographic light-sensitive material containing at least one 1H-pyrazolo[3,2-c]-S-triazole magenta coupler. Next, the present invention will be explained in detail. The present inventors have carried out intensive research aimed at improving the above points, and as a result, we have found that formalin resistance is good, images have excellent light fastness, and also exhibit high color development.
We have now discovered a 1H-pyrazolo[3,2-c]-S-triazole magenta coupler. Specifically, 1H-pyrazolo[3,
2-c]-S-triazole coupler. That is, by substituting a secondary alkyl at the 6th position and a leaving group other than a hydrogen atom at the 7th position in a 1H-pyrazolo[3,2-c]-S-triazole compound, light resistance is greatly improved, We were able to achieve high color development. To explain the leaving group here, the 7th position of the 1H-pyrazolo[3,2-c]-S-triazole compound is the position that undergoes a coupling reaction with the oxidized form of the color developing agent to form a magenta dye. The leaving group is removed by reaction with the oxidized product of the color developing agent. 1H-pyrazolo[3,2-c]- substituted with a secondary alkyl at the 6th position and a leaving group other than a hydrogen atom at the 7th position
Among the S-triazole compounds, the compound represented by the following general formula is more preferable. General formula []

[Formula] In the above general formula [], R ₁ is secondary alkyl,
R ₂ represents a secondary or tertiary alkyl, aryl, or heterocycle, and the alkyl, aryl, or heterocycle may be bonded via an oxygen atom, nitrogen atom, or sulfur atom. Furthermore, the alkyl, aryl, and heterocycles described above may be bonded via the bonding groups listed below. Namely, acylamino, carbamoyl, sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone, sulfonyloxy. X represents a leaving group other than hydrogen that reacts with the oxidized color developing agent and leaves. General formula [] is further represented by general formula []. General formula []

[Formula] In the above general formula [], R ₁ ′ and R ₁ ″ represent a halogen atom, a cyano group, a nitro group, and a group having the same meaning as R ₂ in the above general formula []. R ₂ is a general It represents a group having the same meaning as R ₂ in formula []. Furthermore, R ₁ ′ and R ₁ ″ may be bonded to each other to form a carbocycle or a heterocycle. The groups represented by R ₁ ′ and R ₁ ″ are halogen atoms (e.g., chlorine, bromine, fluorine), straight-chain or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, i-propyl, sec -butyl, n
-butyl, t-butyl, n-octyl, t-octyl, dodecyl, octadecyl, etc.). These groups may further contain substituents (e.g. halogen atom, nitro, cyano, alkoxy, aryl, oxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imide, alkylthio,
It may contain arylthio, aryl, alkoxycarbonyl, and acyl. Specifically, chloromethyl, bromomethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl,
ethylcarbamoylethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenylmethyl, naphthylethyl, ethoxycarbonylethyl, acetylethyl, etc.). Further, the aryl group represents a phenyl or naphthyl group, and may have the substituents shown in the section of the alkyl group above. Further, the heterocycle represents a 5- or 6-membered ring having at least one of a nitrogen atom, an oxygen atom, and a sulfur atom, and may or may not have aromaticity. Examples include pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thiadiazolyl and the like. Further, these may have the substituents shown in the section of the alkyl group. Furthermore, R ₁ ′ and R ₁ ″ may be bonded to each other to form a carbocycle (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, etc.) or a heterocycle (for example, piperidyl, pyrrolidyl, dioxanyl, morpholinyl, etc.).Next Specific examples of R ₁ represented by the above general formula are shown below.

【table】

【table】

【table】 / /
CH ₃ SO ₂ C ₂ H ₅ CONH
The alkyl, aryl, or heterocycle represented by R ₂ is bonded to the above bonding group or via a nitrogen atom, an oxygen atom, or a sulfur atom, such as -OR ₂ ′,

[Formula]-S-R ₂ ',

【formula】

【formula】

【formula】

[Formula] −COR ₂ ′, − OCOR ₂ ′, −COOR ₂ ′,

【formula】

【formula】

[Formula] -SO ₂ R ₂ ′, -OSO ₂ R ₂ ′, etc. can be mentioned. Here, R ₂ ′ represents an alkyl, aryl, or heterocycle, and R ₂ ″ and R ₂ represent a hydrogen atom, alkyl, aryl, or a heterocycle. Note that the heterocyclic group is 1H-pyrazolo[3,2-c]
-S-triazol-3-yl type compound forms a bis-type 1H-pyrazolo[3,2-c]-S-triazole type compound, which is of course a magenta coupler included in the present invention. The leaving group represented by X represents an organic group bonded to the coupling position by a halogen or an oxygen atom, nitrogen atom or sulfur atom. Examples of leaving groups bonded to the coupling position with an oxygen atom include alkoxy, aryloxy, acyloxy, and heterocyclic oxy, and examples of leaving groups bonded to the coupling position with a nitrogen atom include acylamino, diacylamino, and sulfonamide. and a 5- or 6-membered heterocyclic group containing a nitrogen atom thereof, and further examples of leaving groups bonded to the coupling position with a sulfur atom include thiocyano,
Examples include alkylthio, arylthio, heterocyclic thio, arylsulfonyl, and alkylsulfonyl. Next, specific examples of R ₂ represented by the general formula will be shown.

【table】

【table】

_[ Table] Among R ₁ ′ and R ₁ ″, preferred are alkyl and aryl, and more preferred _is unsubstituted alkyl group. good. The most preferred R ₁ is shown below.

【formula】

【formula】

【formula】 【formula】 [] [] []

[Formula] In the formula, n represents an integer of 0 to 4, m represents an integer of 1 to 3, R ₃ is alkyl, aryl, heterocycle; R ₄
represents a hydrogen atom or alkyl; R ₅ represents alkyl, alkoxy, sulfamoyl, sulfonamide, or sulfonyl. Specific examples based on the present invention are shown below, but the present invention is not limited thereto.

[Formula] Next, the synthesis method will be described. Journal of the
Chemical Society, Perkin I 1977, 2047~
The synthesis was carried out with reference to US Pat. No. 2052, US Pat. Synthesis of Compound Example (1) The reaction scheme is as follows. Synthesis of () Suspend 53g of thiocarbohydrazide in alcohol, add 53g of benzaldebide while stirring at boiling. 10 minutes later α-chloroisobutylacetate methyl
89.5 g was added dropwise, and after another 10 minutes, 150 g of hydrazine hydrate was added dropwise over 1 hour. 1 more after dropping
Stir and boil for an hour. Thereafter, insoluble materials are removed and alcohol is distilled off. Add 250 ml of toluene to the residue to crystallize it, and filter it. After thoroughly washing with water and drying, recrystallize with toluene to obtain the desired product. Synthesis of () Add 27g of () to a mixture of 250ml of acetonitrile and 17g of triethylamine and stir to reflux to 37g.
of valmitoyl chloride in 30 minutes. Then reflux for 2 hours. When the reaction solution is cooled, the formed crystals are collected by filtration, thoroughly washed with water, and dried, the desired product can be obtained almost quantitatively. Synthesis of () Add 52 g of () and 20 g of phosphorus oxychloride to 500 ml of toluene and boil under reflux for 2 hours. After that, toluene was distilled off under reduced pressure, and acetonitrile was added to the residue.
Add 300ml and 25.6g of pyridine and boil for 2 hours. Acetonitrile is distilled off, water is added, and the resulting crystals are collected by filtration. After washing with water and drying, recrystallize from acetonitrile to obtain the desired product (). Synthesis of () Add 20g of () to 100ml of glacial acetic acid and 10ml of concentrated sulfuric acid and boil under reflux for 15 hours. After cooling, a caustic soda aqueous solution consisting of 18 g of caustic soda in 100 ml of water is added under stirring. After cooling, the precipitated crystals are collected by filtration and thoroughly washed with water. After drying, use silica gel as a carrier and use benzene/
Purify by column chromatography using acetone. Synthesis of Compound Example (1) 20g of () was dissolved in chloroform, an equivalent amount of N-chlorosuccinimide was added, and the mixture was reacted at 20°C for 1 hour. Thereafter, the reaction solution is washed with dilute alkali and then with water. Chloroform is distilled off, and the residue is purified by column chromatography using benzel/acetone and silica gel as carriers. The target product was confirmed using nuclear magnetic resonance spectroscopy and mass spectroscopy. Other 1H-pyrazolo[3,2-
The synthesis of the C]-S-triazole nucleus itself is an example.
This was carried out according to method (1). (3), (12), and (18) were synthesized according to the method of Example 14 of US Pat. No. 3,725,067. (4) and (19) can be obtained by reacting the corresponding bromine-substituted product with a silver salt of methanesulfonic acid, as disclosed in the above-mentioned US Patent Example 31. (9), (20), and (22) were also able to be synthesized according to the synthesis example in the above US patent. (6), (13), (1
5) and (17) were synthesized with reference to the general synthesis method described in JP-A-59-99437. Silver halide color photographic couplers made using the present invention may also be included. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is a US patent.
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 3891445, West German Patent No. 1547868, West German Application Publication
No. 2219917, No. 2261361, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783, No. 1978, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
No. 51-21827, No. 50-87650, No. 52-82424,
This is described in No. 52-115219, etc. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2369929 and
No. 2434826, No. 3034892, No. 3311476, No.
No. 3458315, No. 3476563 No. 3583971, No. 3591383
No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 1976-
No. 59838, No. 51-26034, No. 48-5055, No. 51-
These are those described in No. 146828, No. 52-69624, and No. 52-90932. As the magenta coloring coupler, the couplers of the present invention may be used alone or in combination of two or more, and in addition, conventionally known pyrazolone compounds, indazolone compounds, cyanoacetyl compounds,
Pyrazolinobenzimidazole compounds, pyrazolotriazole compounds, etc. may be used in combination as appropriate. However, at least one is a coupler of the invention. Furthermore, a colored coupler having a color correction effect and a development inhibitor-releasing coupler (so-called DIR coupler) can be used together with the coupler of the present invention if necessary to improve image quality. Known methods can be used to introduce the magenta coupler of the present invention and each coupler related thereto into the silver halide emulsion layer. Examples include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphide, triphenyl phosphate, tricresyl phosphide, dioctyl butyl phosphide), citric acid esters (e.g. acetyl tributyl citrate), benbrozoic acid esters (e.g. octyl benbrozoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
butyl alcohol, methyl isobutyl ketone,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., 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 magenta coupler of the present invention is added to a silver halide emulsion layer, it is usually added in an amount of 0.005 to 2 mol, preferably 0.03 to 0.5 mol, per mol of silver halide. The dye image formed from the magenta coupler of the present invention itself exhibits strong light resistance, but the light resistance can be further improved by using an anti-fading agent or by providing an upper layer containing an ultraviolet absorber. do. As an anti-fading agent, for example, the US patent
No. 2360290, No. 2418613, No. 2675314, No.
No. 2701197, No. 2704713, No. 2728659, No. 2701197, No. 2704713, No. 2728659, No.
No. 2732300, No. 2735765, No. 2710801, No.
Hydroquinone derivatives described in No. 2816028, British Patent No. 1363921, etc., U.S. Patent No. 3457079,
Gallic acid derivatives described in US Pat. No. 3069262, etc., US Pat. No. 2735765, US Pat.
p-alkoxyphenols described in No. 52-6623, U.S. Pat. No. 3,432,300, U.S. Pat.
No. 3574627, No. 3764337, JP-A-52-35633,
p described in No. 52-147434 and No. 52-152225
-Oxyphenol derivatives, bisphenols described in US Pat. No. 3,700,455, and the like. Examples of ultraviolet absorbers include benzotriazole compounds substituted with aryl groups (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, U.S. Pat. Nos. 3,314,794 and 3,352,681).
benzophenone compounds (e.g. those described in JP-A No. 46-2784), cinnamate ester compounds (e.g. U.S. Pat. No. 3,705,805,
3,707,375), butadiene compounds (e.g., as described in U.S. Pat. No. 4,045,229), or benzoxide compounds (e.g., as described in U.S. Pat.
3700455) can be used.
Furthermore, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used. The silver halide used in the silver halide emulsion used in the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver halide emulsions. This includes anything that is done. The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing color in order to impart the necessary sensitivity in the wavelength range. The colors used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoporacyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Useful sensitizing dyes such as German patents
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No.
No. 2503776, No. 2519001, No. 2912329, No. 2519001, No. 2912329, No.
No. 3656959, No. 3672897, No. 3694217, No.
No. 4025349, No. 4046572, British Patent No. 1242588,
Examples include those described in Japanese Patent Publication Nos. 44-14030 and 52-24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Patents 2688545 and 2977229.
No. 3397060, No. 3522052, No. 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-42375, Japanese Patent Publication No. 52-
No. 110618 and No. 52-109925. Furthermore, the silver halide emulsion used in the present invention is
Various known photographic additives can be included. For example, it is a photographic additive as described in Research Disclosure 17643. As the support for the silver halide photographic material of the present invention, conventionally known supports such as plastic film, plastic laminate paper, baryta paper, synthetic paper, etc. may be appropriately selected depending on the purpose of use. Further, the silver halide color photographic light-sensitive material of the present invention can have any configuration used in the art. The thus constructed silver halide color photographic light-sensitive material of the present invention can be subjected to various photographic processing methods for color development treatment after exposure. The aromatic primary amine color developing agent used in the color developing solution of the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally used at a concentration of about 0.1 g to 30 g per 1 color developer.
Preferably, a concentration of about 1 g to 1.5 g per color developer is used. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxytoluene, 2-amino-3
-oxytoluene, 2-oxy-3-amino-
Includes 1,4-dimethylbenzene and the like. Particularly useful primary aromatic amino color developers are N,N'-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N,N'-dimethyl-p-phenylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,
N'-diethylaniline, 4-amino-N-(2-
(methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate,
Alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzine alcohol, water softeners, thickening agents, and the like can also be optionally contained. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching solution or bleach-fixing solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced during development and converts it into silver halide. At the same time, it has the effect of coloring the uncolored parts of the coloring agent, and its structure is made of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid, and iron,
Coordinated with metal ions such as cobalt and copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid)

[9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) ) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt [18] Propylene diamine Tetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexanediaminetetraacetic acid sodium salt The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and may also contain various additives. I can do it. As additives, in particular alkali halides or ammonium halides,
Rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to contain metal salts and chelating agents. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. , sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath. In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent,
For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. (Example) Next, the present invention will be specifically explained by referring to an example. [Example 1] A silver halide color photographic material was prepared by sequentially coating the following layers on a polyethylene resin coated paper containing anatase type titanium oxide. The amounts added below are per ^100cm2 . (1) 20 mg of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion, and 3 mg of di-octyl phthalate in which 8 mg of Y-coupler* and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing coupler solvent. (2) 12 mg gelatin, 0.5 mg 2,5-di-t-
Intermediate layer containing 2 mg dibutyl phthalate UV absorber solvent in which octylhydroquinone and 4 mg UV absorber* were dissolved. (3) 18 mg of gelatin, 4 mg of green-sensitive silver chlorobromide emulsion, 5 mg of M-coupler* and 2 mg of silver.
of antioxidant* and 0.2 mg of 2,5-di-t
- A layer containing 2.5 mg of dioctyl phthalate coupler solvent in which octyl hydroquinone is dissolved. (4) An intermediate layer containing the same composition as (2). (5) 16 mg of gelatin, 4 mg of silver as a red-sensitive silver chlorobromide emulsion, and 2.0 mg of trichloride in which 3.5 mg of C-coupler* and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved. Layer containing dilphosphate coupler solvent. (6) Gelatin protective layer containing 9 mg of gelatin. Coating aids are added to each layer (1) to (6), and (4)
A gelatin crosslinking agent was added to layer (6). The ultraviolet absorbers (2) and (4) have the following structure.
A mixture of UV-1 and UV-2 was used. As the antioxidant (3), di-t-pentylhydroquinone di-octyl ether was used. The above multilayer photosensitive material was subjected to wedge exposure according to a conventional method and then subjected to the following development treatment. Table 3 shows the Y-coupler, M-coupler, and C-coupler used in each layer and the results. Each sample was measured for magenta density after exposure to white light. Specific sensitivity and light resistance were measured by the following method. 1 Specific sensitivity is the reciprocal of the exposure amount that gives fog density + 0.19 density, and is
It was set as 100. 2 The sample after the color development process was exposed to a xenon fade meter for 5 days, and the percentage of dye remaining after the process at the initial density D=1.0 was shown. Light resistance=Density after 5 days of xenon fade meter irradiation/1.0×100 The development process was as follows. [Development process] Color development 38℃ 3 minutes 30 seconds Bleach fixing 38℃ 1 minute 30 seconds Stabilization treatment 25℃~30℃ 3 minutes or washing process Drying 75~80℃ approx. 2 minutes In each treatment step, The composition of the treatment liquid is as follows. [Color developer] Benzyl alcohol 15ml Ethylene diglycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino- N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total volume to 1, and adjust the pH to 10. Prepare to 20. [Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid and add water Add to make the total amount 1. Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 10g It is clear from Table 3 that the dye image of the coupler of the present invention has excellent light resistance, and also It is also clear that further improvement can be achieved by using . * Ultraviolet absorber UV-1

【formula】 UV-2

[Formula] *Y-coupler Y-1 Y-2 *C-coupler C-1

【formula】 C-2

[Formula] C-3 C-4

【table】

Claims (1)

[Claims] 1 In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in the silver halide emulsion layer, the 3rd position is a secondary alkyl, the 6th position is a secondary alkyl, and the 7th position is hydrogen. 1H-pyrazolo[3,
2-c] A silver halide color photographic material containing at least one magenta coupler based on S-triazole.