JPS61120153A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the resistance of a sensitive material to light and formalin and to improve the color developing property by incorporating a specified 1H- pyrazolo[3,2-c]-s-triazole type magenta coupler into a silver halide emulsion layer. CONSTITUTION:A compound having a group represented by a formula -R1-S-R2 (where R1 is alkylene, and R2 is alkyl) at the 3-position as a substituent is incorporated into a silver halide emulsion layer as a 1H-pyrazolo[3,2-c]-s-triazole type magenta coupler. A compound represented by the formula may be used as said compound. Since the silver halide emulsion layer contains the specified compound, the resistance of the resulting color photographic sensitive silver halide material to light and formalin is increased, and the color developing property can be improved.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler that forms magenta dye-1, which has high color development properties and improved storage stability, particularly durability. More specifically, the novel 1) 1-pyrazolo (3,2-C)
-) A silver halide color photographic material containing a lyazole magenta coupler. (Prior art) In conventional silver halide color photographic light-sensitive materials, exposed silver halide grains are reduced with an aromatic primary amine color developing agent, and at this time, the color developing drug released live is reduced. Coupling of the oxidant with couplers that form yellow, magenta and cyan dyes produces dye #J.
It's a tribute to Il @b. The coupler that has been put to practical use in the past for forming the magenta dye is a pyrazolone type coupler, but this has unfavorable side absorption and is poor in storage stability, especially in formalin gas (formalin resistance). It has the following drawbacks. In order to improve the above-mentioned drawbacks, various 1H-pyrazoloC3,2-C]-kaede-triazole magenta couplers have been proposed, such as U.S. Pat. No. 3,725,06
7, British Patent No. 1,252.418, British Patent No. 1,334.
It is described in No. 515. Of course, the compounds described in both patents are superior to pyrazolone magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and the improvement in light resistance of color development - 1. 11./1. Re5earch Disc
The compound described in Losure 12443 cannot be put to practical use at all in terms of color development. 1H-pyrazolo[3,
Although 2-C]-5-) lyazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, there has been little improvement in light resistance. Also, JP-A-59-97437 and JP-A No. 59-125732
Although the coupler described in the issue has also been improved in color development,
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, but in the former case, compound row 1 described in the specification
Although coupler No. 9 has slightly improved light resistance, it cannot be said that it melts sufficiently. In other words, this 7'1. Well, the 1) (-pyrazolo (3,2-C1-5-) lyazole magenta coupler, which has attracted attention for its lack of side absorption and high formalin resistance, has almost no improvement in the light resistance of dye images. (Objective of the Invention) The object of the present invention is to provide a silver halide color photographic material with good light fastness and formalin resistance, and high color development. (Invention The object of the present invention is to provide a silver halide color photographic light-sensitive material comprising at least one halogenated atomizing agent layer on a support, in which the 3rd position in the silver halide emulsion layer is as follows: 1H-pyrazolo[3,
This is achieved by a silver halide color photographic material containing at least one 2-C]-s-triazole magenta coupler. General formula % Formula % In the formula, R1 represents alkylene and R9 represents alkyl. Next, the present invention will be explained in detail. The present inventors have carried out in-depth research to improve the above-mentioned points, and have found that the formalin resistance is good and the image quality is 1ift.
We have discovered a 1H-pyrazolo["3.2-C]-8-)' riazole magenta coupler with excellent originality and excellent coloring properties. Specifically, the 3rd position has the following general formula: 1H-pyrazolo[3,2-C]-s-triazole substituted with the group shown. General formula % Formula % In the formula, RI represents alkylene, R, ff alkyl. That is, 1H-pyrazolo(3, When the 3-position of 2-C]-s-triazole was substituted with a group represented by the above general formula, it was possible to achieve a significant improvement in light resistance and high color development. is substituted with a group represented by the above general formula, and the 7th position, which is the cup 1 position with the oxidation product of the color development I main system, is substituted with a leaving group other than a hydrogen atom, resulting in light resistance and color development. The alkylene represented by R8 is alkyl, all<f
l+JL haphenyl], halogen cyanide, and further substituted with a carbonyl substituent such as alkoxycarbonyl, acyl, carbamoyl, etc., and a substituent bonded with a hetero atom such as nitro, alkoxy, amolthio, dialkylamino, etc. It's okay. The alkyl represented by R1 represents a branched secondary or tertiary alkyl in the history of a primary alkyl.A primary alkyl represents an alkyl in which two hydrogen atoms are bonded to the root carbon, and a secondary alkyl represents an alkyl in which two hydrogen atoms are bonded to the root carbon. represents an alkyl having one bonded to it, and tertiary alkyl represents an alkyl having no hydrogen bonded to the root carbon. Alkyl represented by R2 is an aryl, heterocycle, halogen, cyano, a substituent bonded to carbonyl such as alkoxycarbonyl, acyl, carbamoyl, etc., and a heteroatom such as nido-s alkoxy, alkylthio, dialkylamino, etc. It may be substituted with a bonding substitution. Note that the heterocyclic group is 1H-pyrazolo(3,2-C)-3-
When a triazol-3-yl compound is used, it forms a bis-type 1H-pyrazolo(3,2-C]-'-triazole compound, which is of course a magenta coupler included in the present invention. At the 7th coupling position Examples of leaving groups other than the bonded hydrogen atom include halogen, and further organic groups bonded to the coupling position with an oxygen atom, nitrogen atom, or sulfur atom.Leaving groups bonded to the coupling position with an oxygen atom Examples of the leaving group include alkoxy, aryloxy, heterocyclic oxy, etc., and leaving groups bonded to the cup ll blowfish position at the nitrogen atom include acylamino, diacylamino, sulfonamide, and 5-membered 6-membered groups including acylamino, sulfonamide, and their hydrogen atoms. In addition, examples of the membered heterocyclic group and the like that are bonded to the coupling position with a sulfur atom include thiocyano, alkylthio, arylthio, heterocyano, arylsulfonylalkylsulfonyl, etc. Among the present invention, More preferably, it is represented by the following general formula: The definitions of R and R have already been described. RFi alkyl represents an aryl heterocycle, and alkyl includes primary alkyl, branched secondary and tertiary alkyl, and of course cycloalkyl. The aryl is preferably substituted or unsubstituted phenyl, and the heterocycle is specifically exemplified by furan-broken thiofuran. Specific sequences based on the invention are shown below, but the invention is not limited thereto. CH. OH. ah.
1H-pyrazolo(3,2-C)-3- after synthesizing l
Synthesis of triazole FiResearch Discl
osure12443, and Journal of t
he Chemica18ocJety, Perk
Jn I 1977, 2047-2052, and further [Introduction of a leaving group at the 7-position is described in US Pat. No. 15, 3.725.0.
No. 67 and JP-A-59-97437 were referred to. Typically (1) 3-octadecylthio- required for O&
A method for synthesizing 2-methylpyropionic acid is shown. Reaction scheme KOHf (CJ Sodium acetate 36JF is heated and dissolved in 25 cc of water. Octadecyl mercaptan 28611, methyl methacrylate 1201 hydroquinone II and alcohol 600 cc are added to this and stirred and refluxed for 6 hours. The alcohol and excess methyl methacrylate are distilled off. Add water 50011j to the residue and extract with toluene. Distill the toluene under reduced pressure to obtain the crude target product. ITLC
Because the purity was such that there was no problem in using it for the next reaction, it was not particularly loaded. Synthesis of (I[) Crude (I) 370 Ii was mixed with 600 CC of alcohol.
In addition to this, add 120.9 ml of potassium hydroxide to 600 cc of water.
Dissolve VC and add to the above alcohol. Stir and reflux for 1 hour. The alcohol was distilled off, and the remaining liquid was poured into 3.5 liters of ice water containing 250 cc of salt Cal. The crystals that can be precipitated are collected by filtration, washed with methanol, and then dried. Recrystallize from hexane to obtain the desired product (I[). (4) , (8) , (15) K at R, -8
-R, -C00H1d Re5search Discl
The synthesis reaction scheme of chemical compound series (1), which could be synthesized by the method described in osure 24512 (84), is as follows. (I) (II) Synthesis of (I) CI) itself is published in the Journal of the C
11enica18ocietl Perkin
I, 1977*2047-2052, and was synthesized according to that method. Synthesis of (IF) 461 CI) was suspended in 5004 acetonitrile,
Triethylamine 30I is added to this, and while stirring while boiling, the acid chloride prepared from 102.9 acid with thionyl chloride is added dropwise. Then, reflux for (9) minutes. After cooling, the formed constant crystals are collected by filtration, thoroughly washed with water, and dried, and the target substance is almost precisely absorbed. Synthesis of (III) 91.9 of (II) and 26.9% in 700M toluene.
8. Boil and reflux the phosphorus oxychloride (II) for 4 hours. Thereafter, toluene was distilled off under reduced pressure, and 70017 acetonitrile and 40Ii pyridine were added to the residue, followed by boiling and refluxing for 1.5 hours. Acetonitrile is distilled off, water is added, and the resulting crystals are collected by filtration. After washing with water and drying, the product is recrystallized from acetonitrile to obtain the desired product (III). Synthesis of 55Il (III) with glacial acetic acid 5001j, a sulfuric acid wa
Add to a mixture of 10 gs water and boil under reflux for 8 hours. A caustic soda aqueous solution consisting of 50 g of cooled condensate and 90 g of caustic soda was stirred and separated. The precipitated crystals are collected by filtration and thoroughly washed with water. Dry to obtain the target product (IV). Synthesis of Compound Example (1) Dissolve (IV) of M[' in chloroform,
Add chlorsuccinimide and react at room temperature for 1 hour. Thereafter, the reaction solution is washed with dilute alkali and then thoroughly washed with water. When chloroform is distilled off and left behind, benzene/
Purify by column chromatography using acetone, silica, and Kagel as carriers. Confirm the target! ! ! were conducted using nuclear magnetic resonance spectroscopy and mass spectroscopy. Synthesis of compounds (3), (9), (13) #1R
1H-pyrazolo (3,2-C1-5-triazole nucleus is formed and a leaving group is introduced in accordance with esearchDisclosure 12443 Fi U.S. Patent No. 3,72
5.067 and JP-A-59-99437. (3), (9), and (13) were removed.<1H-pyrazolo[3,2-C]-s-triazole nucleus was prepared according to the method in column (1). (4), (7), (14), (15),
The introduction of leaving groups in (16) and (17) is also described in U.S. Pat.
Compare with reference to No. 7. The silver halide color photographic light-sensitive material prepared using the present invention may contain a conventionally used dye-forming coupler. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are U.S. Pat. Nos. 2.875.057 and 3,265.5.
No. 06, No. 3 408.194, No. 3,551.15
No. 5, No. 3.582.322, No. 3,725.072
No. 3,891.445, West German patent 1,5. s7゜868, West German Published Application No. 2,219.917, No. 2
, 261, 361 Mai, No. 2,414,006, British Patent 1,, s25, O20, Special Publication No. 1983-107
No. 83, JP-A-47-2613.3, JP-A No. 48-731
No. 47, No. 51-102036, No. 50-6341, No. 50-123342, No. 50-130.442, No. 51-21827, No. 50-87650, No. 5
Phenol compounds, naphthol compounds, etc. can be used as cyan color-forming couplers such as those described in U.S. Pat. Nos. 2-82424 and 52-115219. , 2,434
．． No. 272, No. 2,474.29:3, No. 2,521
, No. 908, No. 2,895゜826, No. 3, 034
, No. 892, No. 3,311.476, No. 3, 45
8, No. 315, 3゜476, 563, 3.5
83, No. 971, No. 3.591.383, No. 3, 7
No. 67.411, No. 4,004,929, West German Patent Application (OL8) No. 2.414.830, No. 2, 454
, No. 329, JP-A-48-59838, JP-A No. 51-2
No. 6034, No. 48-5055, No. 51-14682
No. 8, No. 52-69624, and No. 52-90932. As the magenta coloring coupler, the coupler of the present invention may be used alone or in combination of two or more types of #-t, and also conventionally known pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, pyrazolino Penzimidazole compounds, pyrazolotriazole compounds, etc. may be used in combination as appropriate. However, at least one is a coupler of the invention. In addition, colored couplers having a color correction effect, and furthermore, color inhibitor releasing couplers (so-called DIR couplers) for improving image quality can be used together with the couplers of the present invention as required. In order to introduce each coupler into the silver halide emulsion layer, known methods such as those described in U.S. Pat. No. 2,322,027 can be used.
dibutyl phthalate, dioctyl phthalate, etc.), phosphate esters (diphenyl 7-mole 7-ate, ) I + phenyl pho-
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. tributyl benzoate),
(e.g., diethyl laurylamide), fatty acid esters (e.g., dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (e.g., tributyl trimesate), etc., or with a boiling point of about 1°C to 15°C.
Organic solvent at 0°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl gropionate, 2
After dissolving in butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl selonol 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. IT Special Publication No. 51-39853, Japanese Patent Publication No. 51-5994
Dispersed beds of polymers as described in No. 3 can also be used. When the magenta coupler of the present invention is added to a silver halide emulsion, it is usually 0.005 to 2.0% per mole of silver halide.
It is added in moles, preferably in the range of 0.03 to 0.5 moles. Dye-1 formed from the magenta coupler of the present invention itself exhibits strong light resistance, but the use of an anti-fading agent and the provision of a layer containing an ultraviolet absorber on the upper layer further improves the light resistance. improves. As an anti-fading agent, for example, U.S. Patent No. 2.360.2
No. 90, No. 2,418.613, No. 2675.314
No. 2,701.197, No. 2.704.713, No. 2,728.659, No. 2,732.300,
2,735.765, 2,710.801, 2,816.028, British Patent 1.363.921
Hydroquinone derivatives described in US Pat. No. 3.
Gallic acid derivatives described in No. 457.079, No. 3.069.262, etc., US Pat. '
i, No. 765, No. 3.698.909, Special Publication No. 4
p described in No. 9-20977 and No. 52-6623
-Fulkyl esters, rice [j.3, 432.300
No. 3,573.0 FlO, No. 3゜574.627
No. 3,764.337, JP-A-52-35633
No. 52-147434 and No. 52-152225, p-oxyphenol visiting conductor, U.S. Patent 3
, 700, 455, and the like. Examples of ultraviolet absorbers include benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533
3.794), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314.794, U.S. Pat. No. 3,352)
．． 681), benzophenonates (for example, those described in JP-A No. 46-2784), and cinnamate compounds (for example, U.S. Pat. Nos. 3,705,805 and 3,707). No. 375), butadienated fabrics (as described in U.S. Pat. No. 4,045.229), and benzoxidol compounds (for example, as described in U.S. Pat. No. 3,700.455). Furthermore, U.S. Pat. No. 3,499,762
JP-A 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. The silver halide used in the present invention is spectrally sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. The pigments used include cyanine pigment, merocyanine pigment, *shade 7
Included are anine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinonol color ranges. Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 50, U.S. Patent No. 2,231.658, U.S. Patent No. 2,493
．． No. 748, No. 2,503.776, No. 2,519.
No. 001, No. 2, No. 912, No. 429, No. 3, 6
No. 56.959, No. 3,672゜897, No. 3,69
No. 4,217, No. 4,025, No. 349, No. 4,04
6.572, British Patent No. 1,242.588, Japanese Patent Publication No. 44-14030, and Japanese Patent Publication No. 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. A typical example is U.S. Patent No. 2,688.545, U.S. Pat.
77.229 No. 3, 397, 060, No. 3,
No. 522,052, No. 3, No. 527, No. 641, No. 3
, 617.293, 3, 628, 964, 3,666.480, 3.672898, 3,
No. 679.418, No. 3,703.377, No. 3.7
fi 9.301, fi 3゜814.609, fi 3,8
No. 37.862, No. 4.026.707, British Patent 1
, No. 344.281, No. 1,507.803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Unexamined Patent Publication No. 52-1972
-1.10618 and No. 52-109925. Furthermore, the silver halide emulsion used in the present invention can contain various known photographic additives. l1 column Re5search Disclosure 1764
Photographic additives such as those described in No. 3. As the support for the silver halide photographic material of the present invention, conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. may be appropriately selected depending on the purpose of use. Further, the silver halide color photographic multi-component material of the present invention can be of any type used in the art. In the silver halide color photographic process of the invention, various photographic processing methods are used for color development after exposure. Aromatic Li41 used in the color development acupuncture solution in the present invention
The amine color-forming agents include those known and widely used in various color photographic processes. These current abrasives include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than in the free state. Also, these compounds are
Color Developer II is generally used at a concentration of about 0.1, F to about 30.9 degrees F for Solution IIt, preferably from about IN to about 1.51 for Color Developer 1 Solution 1). Examples of aminophenol-based tII agents include 〇-aminophenol, p-aminophenol, and 5-aminophenol.
These include 2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1°4-dimethylbenzene, and the like. Particularly useful 11th class aromatic amine color developing agents are N, N
'-Dialkyl-p-fuynylenediamine-based @- compounds, in which the alkyl group and phenyl group may be substituted with any tti substituent.Among them, particularly useful compound series include N, N/ -diethyl-p-phenylenediamine hydrochloride, N-methyl-p-7enylenediamine salt eIR salt, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl- -dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoanili7
ft1ly R1 salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N
, N'-diethylaniline, 4-amino-N-(
Examples include 2-methoxyethyl]-N-ethyl-3-methylaniline-p-toluenesulfonate. In addition to the above-mentioned primary aromatic amine color developer, the color developer solution used in the process of the present invention further includes a color developer.
Various components normally added to 1I liquid, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl Alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developing solution is usually above 7, most commonly about 1.
0 to about 13. In the present invention, after color development treatment, processing is performed with a processing liquid having fixing ability, but if the processing liquid having fixing ability is a fixing liquid, whitening treatment is performed before that. A metal complex salt of an organic acid is used as the bleaching agent used in the bleaching solution and the bleach-fixing solution, and the metal complex salt oxidizes the metallic silver removed by the current IJt to convert it into silver halide. It has the effect of coloring the uncolored part of the coloring agent at the same time as changing, and its structure is made of aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid, and contains iron, cobalt,
It is coordinated with copper ions such as copper. The most preferred organic acids used to form a metal complex of such an organic acid include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or amitubo-carpoy
@d Alkali metal salts, ammonium salts, and shukesui tetravalent amine salts are fine. Specific representative sequences of these include the following. [1] Double diamine tetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N, (β-oxyethyl) -N,
N', N'-) diacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroacetic acid (7t)
is tartaric acid)

[9] Ethyl ether diamine tetraacetic acid [10]
Glycol ether diamine tetrarn#1 [11]
Ethylenediaminetetrapropionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriamine pentaacetic acid bentanatrium salt [17] ] Ethylenediamine-N- β-oxyethyl) -N, N', N'-triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] The liquid contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and can also contain various additives. As additives, in particular alkali-11 halides or ammonium halides, potassium bromide,
Re-halogenation of sodium bromide, sodium chloride, ammonium bromide, 4J, metal salts, chelating agents, and pHMfdR agents such as borates, oxalates, acetates, carbonates, and phosphorus. , alkylamines, polyethylene oxides, etc., which are commonly added to bleaching solutions, can be added as appropriate. Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, binitrous @IIC
potassium metabisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, metabisulfite)
Sulfites such as IJ Tsum, d#, borax, sodium hydroxide, potassium hydroxide, sodium 11um carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium 11um acetate, ammonium hydroxide, etc. p consisting of ca
It can contain one or more H buffers. When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with the LCFI white fixer 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, Hydrogen peroxide, bromine salts, persulfates, etc. may be added as appropriate. (Implementation Series) Next, the present invention will be explained with reference to implementation sequences, but the present invention is not limited to these. [Implementation row-1] The magenta coupler of the present invention and the comparative coupler shown in Table 1 were each taken in an amount of 0.1 mol per mol of silver, and tricresyl phosphate of 1 times the weight of the coupler and 3 Add the same amount of ethyl acetate and warm to ω°C to completely dissolve. This solution was mixed with 120% water bath solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
The mixture was warmed with 1200 g of an aqueous gelatin solution containing 500 g of gelatin, and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was converted into a green-sensitive silver iodobromide emulsion (containing 6 mol of silver iodide).
4 kg, and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol = 1:
1) 120#E7? A sample was prepared by drying the cloth on a subbed transparent polyester paste.
(added to the coated silver/100 d) The sample of 7'L7 thus obtained was subjected to 9-edge exposure according to the conventional method, and then subjected to the following phenomenon treatment. The results are shown in Table 1. . [Processing process] Color development solution Seki'C 3 minutes 15 seconds Bleaching solution A℃ 4 minutes w seconds Water washing A℃ 3 minutes 15 seconds Fixing solution A℃
Wash water for 4 minutes ℃ 3 minutes 15 seconds Stabilizing solution ℃
Drying for 1 minute (capital) seconds, 47°C ± 55°C, 16 minutes, blade seconds. The composition of the processing liquid used in each processing step is as follows. [Color-forming gland fluid composition] [Bleaching solution composition] [Stabilizing solution composition] [Stabilizing solution composition] Table 1 1) Comparative sensitivity is compared using the reciprocal of the exposure area giving a rating of Capri yield + 0.1 Using coupler 1, north sample 11 was set to 100. 2) After placing the sample in a sealed container containing 6cc of 0.9% formalin aqueous solution at 30°C and 626RHK temperature and humidity control for 3 days, color development was carried out.For comparison, a sample treated with formalin powder was also developed. I imagine. 3) Color development (The sample after image processing was irradiated with a xenon fade meter for 8 days, and Comparative coupler 1, Comparative coupler 2, Comparative coupler 3, which showed residual dye retention after processing at initial degree D = 1.0) It can be seen from Table 1 that the couplers of the present invention are improved over the comparative couplers in three respects: color development, resistance to Forma 11, and light resistance. [Run-2] Sample 11 in Row-1 After performing wedge exposure in the same manner as in Samples 1 to 19, the following 11 processing was performed.The results are shown in Table 2.The measurements of specific sensitivity and light resistance were carried out on the same floor as in Actual M Row 1. Obstacle Treatment Technique] Color development 1° C. 3 minutes force seconds bleaching A degree C. 1 minute force seconds drying 75-80° C. about 2 minutes In each treatment step, the composition of the treatment liquid used was as follows. [Color developing solution] [Bleach constant solution] Ammonium sulfite (40% solution) 27.5 m Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, add water to make a total of 1
Let it be tll. [Stabilizing liquid] 5-chloro-2-methyl-4-inothiazolin-3-one 1. OI ethylene glycol 10. 9 Table 2 [Implementation row-3] Each of the following layers is made of a material containing anatase-type titanium oxide.
A silver halide color photographic material was prepared by coating on ethylene resin coated paper in the following order. The following additions IFitooc! Indicates the winning number. (1) Add! n9+7) 7t' latin, 5 as silver fine
m9 g-sensitive silver chlorobromide emulsion, and 3η di-octyl lactate igra solvent in which 2.5-di-t-octylhydroquinone of 0.1 and 1 g of Y-force of n9 was dissolved. l1L (21121R9f) Gelatin, 0.51v 2.5-
An intermediate layer containing di-t-octylhydroquinone and a dibutyl phthalate ultraviolet absorber agent of fc2Fn9 in which an ultraviolet absorber of 4 In9 is dissolved. (Gelatin of 3118■, green sensitivity 4 of No. 41 as silver border)
Silver bromide emulsion and M-coupler of 5In9 and 21n9
1-A (4) with the same Mi composition as in (2) containing 2,5 m9 of dioctyl phthalate coupler bath medium in which rice antioxidant and 0.2 to 2,5-di-1-octylhydroquinone were dissolved. Including middle class. (5116 ~ gelatin, 4 m9 of red-sensitive salted silver bromide emulsion as a silver base, and 3.5 M9 of C-coupler and H0
．． A layer containing 2,0 to tricresyl phosphate coupler solvent in which 111 ip of 2,5-di-t-octylhydroquinone was dissolved. (6) Gelatin protection containing 9 ~ gelatin (1
) to each no in (6)? 'i spreading aid was added, and gelatin crosslinking agent was added to (4) and (6) iv/i. As the ultraviolet absorber in (2) and (4), UV-1 and UV-2 having the structure described above were mixed and used. Di-t-pentylhydroquinone di-octyl ether was used as the anti-aging agent (3). The above multilayer photosensitive material was processed in the same manner as in Example 2.
Used in each layer: fcY-force puller, M-coupler, C-
The couplers and their results are shown in Table 3. Each sample was white-light. 4 was measured. Measurement of relative sensitivity and light resistance was carried out in the same manner as in 1. t7
From Table 3, it is clear that the coupler of the present invention has excellent light resistance as dye-1. It is also clear that the improvement can be further improved by using Mine ultraviolet Iwao absorber + Y-coupler =! g 3 Written amendment to the procedure dated November 26, 1975 2 Name of the invention Silver halide color photographic light-sensitive material 3 Relationship to the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Issue name (1
2)) Roku Konishi Photo Industry Co., Ltd. 4, Agent 191 Address 1 Sakura-cho, Hino-shi, Tokyo Voluntary 6 Statement subject to amendment 7 Contents of amendment

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one layer of silver halide emulsion on a support, in the silver halide emulsion layer, the 3-position is a group represented by the following general formula. A silver halide color photographic material containing at least one substituted 1H-pyrazolo[3,2-C]-s-triazole magenta coupler. General formula -R_1-S-R_2 [In the formula, R_1 represents alkylene and R_2 represents alkyl. ]