JPS61120152A - 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(O)n- R2 (where R1 is alkylene, R2 is alkyl or aryl, and n=1 or 2) 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 ('Industrial Field of Application) The present invention provides a silver halide color containing a magenta coupler which forms a magenta dye image with high color development and improved storage stability, especially light fastness. Regarding photographic materials.

More specifically, the novel 1H-pyrazolo(3,2-C)-8
- A silver halide color photographic material containing a triazole magenta coupler.

(Conventional wave W) In conventional silver halide color photographic light-sensitive materials, photosensitive silver halide grains are reduced with an aromatic primary amine color developing agent, and the color developing agent produced at this time is reduced. Dye images are obtained by coupling the oxidant with couplers that form yellow, magenta, and cyan dyes.

The couplers that have been used in practice to form the magenta dye are pyrazolone couplers,
This has disadvantages in that it has undesirable side absorption and is poor in storage stability, particularly in resistance to formalin gas (formalin resistance).

In order to improve the above drawbacks, various 1H-pyrazolo(3,2-C)-S-triazole magenta couplers have been proposed. For example, U.S. Patent 3,725,
067, British Patent No. 1,252゜418, British Patent No. 1,33
No. 4,515.

The compounds described in both patents are of course superior to pyrazolone-based magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and there has been little improvement in the light resistance of chromogenic images. R-esatz
The compound described in r-chDisc3osure 12443 cannot be put to practical use at all in terms of color development.

1H-Pisshiwa 1 described in JP-A-58-42045:
3.2-C)-S-Triazole type magenta couplers have been significantly improved in terms of formalin resistance and color development, but light resistance has hardly been improved.

Also, JP-A-59-99437, JP-A No. 59-125732
Although Kab b- 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 merely improved by the additives used in combination. However, the former compound described in the specification Example 1
Coupler No. 9 has slightly improved light resistance, but it cannot be said to be sufficient.

In other words, 1H-pyrazolo (3,2-
C) It can be said that little improvement has been made in the light resistance of dye images of -S-triazole magenta couplers.

(Object of the invention) The object of the present invention is to have good light resistance and formalin resistance,
Moreover, it is an object of the present invention to provide a silver halide color photographic material with 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 3rd position is as follows: 1H-pyrazolo (3,
This is achieved by a silver halide color photographic light-sensitive material containing at least one 2-C)-S-triazole magenta coupler.

1 Formula % Formula % In the formula, R1 represents alkylene, R2 represents alkyl and aryl, and n represents 1t or 2.

Next, the present invention will be explained in detail.

The present inventors have carried out intensive research aimed at improving this point, and as a result, we have found that 1H-pyrazolo (3,2
-C) A -S-triazole magenta coupler has been discovered.

That is, when the 3-position of 1H-pyrazolo(3,2-C)-8-triazole is substituted with a group represented by the above general formula, it is possible to achieve a large improvement in light resistance and high color development. done.

When the 3rd position is substituted with a group represented by the above general formula and the 7th position, which is the coupling position with the oxidized color developing agent, is substituted with a leaving group other than a hydrogen atom, light resistance and color development properties are improved. It exhibits even more preferable performance.

Alkylene represented by R1 is alkyl, aryl (for example, 7-El), hexagen, cyano, a substituent bonded to carbonyl such as alkoxycarbonyl, acyl, carbamoyl, etc., and furthermore nitro, alkoxy, alkylthio, It may be substituted with a substituent bonded through a heterotetra atom such as dialkylamino.

The alkyl represented by R1 represents a primary alkyl, or a branched secondary or tertiary alkyl. Primary alkyl represents an alkyl with two hydrogens bonded to the root carbon, secondary alkyl represents an alkyl with one hydrogen bonded to the root carbon, and primary and tertiary alkyl represents an alkyl with no hydrogen bonded to the root carbon. represents an alkyl group.

The alkyl represented by R3 is an aryl, a heterotetracyclic ring, a halogen, a cyano, a substituent bonded with carbonyl such as alkoxycarbonyl, acyl, carbamoyl, etc., and a heteroatom such as nitro, alkoxy, alkylthio, dialkylamino, etc. It may be substituted with a bonding substituent.

Note that the heterocyclic group is 1H-pyrazolo(3,2-C) -
8-) When IJ is an azol-3-yl compound, it forms a bis-type 1H-pyrazolo(3,2-C)-S-triazole compound, which is of course a magenta coupler included in the present invention.

Examples of the aryl represented by - include phenyl, naphthyl, etc., and these include alkyl 7'+rogen, cyano,
Furthermore, substituents bonded with carbonyl such as alkoxycarbonyl, amyl, and bamoyl, furthermore nitre,
It may be substituted with a substituent bonded to a heteroatom such as alkoxy, alkylthio, or dialkylami7.

Examples of the leaving group other than a hydrogen atom bonded to the 7-coupling position include halogen, and further organic groups bonded to the coupling position through 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 and diacyl. Amino, sulfonamide, and their nitrogen atom-containing 5- or 6-membered heterocyclic groups, etc., and leaving groups bonded to the coupling position at the sulfur atom include thiocyano, alkylthio, arylthio, heterotetracyclic thio, etc. , arylsulfonyl, alkylsulfonyl, etc., are more preferably represented by the following general formula "1 e The definition of R1 has already been described. represents a group, which has also been described above.

R represents an alkyl, an aryl, or a heterocyclic ring, and the alkyl represents a primary alkyl, and furthermore a branched secondary or tertiary alkyl. Of course, cycloalkyl is also included. Moreover, this alkyl may be substituted with the substituent listed for -.

The aryl preferably represents substituted or unsubstituted phenyl, and the heterocycles include specifically a heptene ring, a thiophene ring, and the like.

Specific examples based on the present invention are shown below, but the present invention is not limited thereto.

In addition, 1B-pyrazolo[3,2-c3-
The s-triazole magenta coupler is desirably non-diffusible and preferably has a molecular weight of over 450.

Fortune telling 3 (2)080. CI(.

C) 11 L:aH
syCB.

(tO) ’ (13) 0II.

II3 Next, the synthesis method will be described.R,-8(0)n-R,-C
1H-pyrazolo, (3,2-C) after synthesis of oon
-S-Triazole synthesis is available at Re5eurch Dis
Closure12443 and Journal of
the Chemical 5ocietyPerk
ln 1 1977, 2047-2052, and the introduction of a leaving group at the 7-position was carried out according to U.S. Patent No. 3,725,06.
No. 7 and JP-A-59-99437 were referred to.

R, -5o, -RI-Coon are all corresponding R
, -8-R, -COO)I was obtained by oxidizing with hydrogen peroxide according to the method described in JP-A-47-24321.

R, -8o-R, -COOH is in ice vinegar, R, -8-R
, -Coo) and hydrogen peroxide in an equimolar cold reaction.

Synthesis of compound example (1) The reaction scheme is as follows.

CH.

(I) Compound Example U) Synthesis of (1) (1) itself is published in the Journal of the Ch.
chemical 5ocietyPerkin 1, 1
977, 2047-2052, and was synthesized according to that method.

Synthesis of (1) 'J21 (1) was dispersed in 1/1 acetonitrile, 60 g of triethylamine was added, and the mixture was boiled and refluxed, and a chloride solution of acid 2221 diluted with thionyl chloride was added dropwise. The capital will then be recycled. The crystals formed after cooling are
Remove, wash thoroughly with water, and dry. The objective is obtained with a yield of 80%.

Synthesis of (It) in toluene of 1.51! (phantom and 53.
Add phosphorus oxychloride (5) II and boil and reflux for 5 hours.

After that, toluene was distilled off and the residue was 1.51! of acetonitrile and 5oII of pyridine are added and boiled at reflux for 1.5 hours. Acetonitrile is distilled off, water is added, and the resulting crystals are collected. After washing with water and drying, recrystallize with acetonitrile to obtain the desired product (@).

(Shun no Synthesis 130, f (wood vinegar! l!1/, concentrated sulfuric acid 100M
Add to the paddy cod mixture and boil under reflux for 10 hours. A caustic soda aqueous solution consisting of left-to-cool water 11 and caustic soda 1801 is poured under stirring. Collect the precipitated crystals and wash thoroughly with water. Dried to obtain the desired product (seasonal).

Synthesis of Compound Example (1) 2 ol of (2) is dissolved in Ritashiform, an equivalent amount of N-chlorosuccinimide is added, and the mixture is reacted at room temperature for 1 hour. Thereafter, the reaction solution is washed with a dilute alkali and then thoroughly washed with water. Chloroform is distilled off, and the residual liquid is purified by catem chromatography using benzene/acetone and silica gel as carriers. Confirmation of target object.

The analysis was performed using wax resonance spectroscopy and mass spectroscopy.

Synthesis of compounds (2), (6), (L Re5e
The 1H-pyrazolo[3゜2-C)-9-triazole nucleus was synthesized in accordance with Arch Dis-closure 12443, and the introduction of a leaving group was described in U.S. Pat.
The example described in No. 67 and JP-A-56-99+37 were followed.

(2), (1H-pyrazolo() other than (l)
The 3,2-C)-S-triazole nucleus was synthesized according to the method of Example (1).

(5), (15), (17), (18)
, The introduction of the leaving group in (19) is also described in U.S. Pat. No. 3,72
No. 5,067 and JP-A No. 59-99437 were referred to.

The silver halide color photographic light-sensitive material prepared using the present invention may contain a conventionally used dye-forming coupler.

As the yellow color-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, benzyla-7tanilide-based and pivaloylacetanilide-based compounds are advantageous. Specific examples of yellow-color-forming couplers that can be used include: U.S. Patent No. 2,875,057, 3,
No. 265,506, No. 3.408,194, No. 3
, No. 551, 155, same: a, No. 582, 322,
No. 3,725,072, No. 3,891,445,
West German Patent No. 1,547,868, West German Application Publication No. 2,21
No. 9,917, No. 2,261,361, No. 2,414
, No. 006, British Patent No. 1,425,020, Special Publication No. 5
No. 1-10783, Japanese Patent Publication No. 47-26133, No. 4
g-73147, 51-102036, 50-
No. 6341, No. 50-123342, No. 50-, No. 52-82424, No. 52-115219, etc.

Phenol is a cyan coloring coupler! Compounds, naphthol compounds, etc. can be used. Specific examples are U.S. Pat. Nos. 2,369,929 and 2,434,2.
No. 72, No. 2,474,293, No. 2,521,9
No. 08, No. 2,895,826, No. 3,034,8
No. 92, No. 3,311,476, 1! tt3,45
No. 8,315, No. 3,476.563, No. 3,58
No. 3,971, No. 3,591,383, No. 3,76
No. 7.411, No. 4,004,929, West German Patent Application (OL8) No. 2,414,830, No. 2゜454.3
No. 29, flPw! No. 48-59838, 1tt151
-26034, 4g-5055, 51-146
No. 828, No. 52-69624, No. 52-9093
This is the one described in No. 2.

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, indashilon compounds,
A cyanoacetyl compound, a pyrazolinopenzimidazole compound, a pyrazolotriazole compound, or the like 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 furthermore, a development inhibitor releasing coupler (so-called DIR coupler) for improving image quality can be used together with the coupler of the present invention, if necessary.

The magenta coupler of the present invention and related couplers can be introduced into the silver halide emulsion layer by known methods, such as those described in U.S. Pat. No. 2,322--. The method described in No. 027 can be used.

For example, phthalate alkyl esters (dibutyl phthalate, dioctyl heptatalate, etc.), phosphoric acid esters (
Diphenyl 7t sulfate, triphenyl phosphate, tricresyl 7m 7ate, dioctyl butyl 7
t sulfate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azeley) ),
) rifsinate esters (tributyl trimesate), or organic solvents with a boiling point of 30"C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, propionic ethyl alcohol, secondary butyl alcohol, methylin After dissolving in butyl ketone, 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.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using polymers described in No. 3 can also be used.

When the magenta coupler of the present invention is added to a silver halide emulsion layer, it is usually o, oos to 1 mole of silver halide.
It is added in an amount of 2 mol, preferably in the range of 0.03 to 0.5 mol.

Although the dye image formed from the magenta coupler of the present invention itself exhibits strong light resistance, an anti-fading agent is used in combination. By providing a layer containing an ultraviolet absorber on the upper layer of the strawberry, the light resistance is further improved.

As the anti-fading agent, for example, US Pat.
No. 90, rWJ2, 418, 6138, l'i'12
, No. 673314, No. 2,701,197, No. 2,7
No. 04,713, No. 2,728,659, No. 2,73
No. 2,300, No. 2,735,765, No. 2,710
, No. 801, No. 2.816,028, British Patent No. 1, 3
Hydroquinone derivatives described in No. 63,921 etc.
U.S. Patent No. 3,457,079, U.S. Patent No. 3,069,262
Gallic fist derivatives described in US Pat. No. 2,735, etc.
, No. 765, 3,698. Mo No. 09, special public service 1977-2
No. 0977.

p-alfukidiphenols described in US Pat. No. 52-6623, US Pat. No. 3,432,300, US Pat. No. 3,573
．． No. 050, No. 3,574,627, No. 3°764.
337, JP-A No. 52-35633, JP-A No. 52-147
434 and p-oxy7-el derivatives described in US Pat. No. 52-152225, US Pat. No. 3,700.

There are bisphenols described in No. 455.

As ultraviolet absorbers, for example, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533
, 794), 4-thiazolidone compounds (
For example, U.S. Patent Nos. 3,314,794 and 3,352,
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), silicon acid ester compounds (e.g., U.S. Pat. No. 3,705,805,
3,707,375), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., those described in U.S. Pat. No. 3,700,455). ) can be used. Further, 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 may include ordinary silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Includes anything used.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity in the required wavelength range. Dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231,658, U.S. Patent No. 2.493
, No. 748, 2,503. '776, same 2゜519
．． No. 001, No. 2,912,329, No. 3,656°959, No. 3,672,897, No. 3,694,2
No. 17, No. 4,025,349, No. 4,046,57
No. 2, British Patent No. 1,242,588, Special Publication No. 1977-1
No. 4030, those described in No. 52-24844 [
I can list them.

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. Patent No. 2,688,545;
．． 977.229, 3,397,060, 3゜522.052, 3,527,641, 3,6
17゜293, 3,628,964, 3,66
6.480, 3,672,898, 3,679
, No. 428, No. 3,703,377, No. 3,769,
No. 301, No. 3.814,609, No. 3,837,
No. 862, No. 4゜026.707, British Patent No. 1,34
No. 4,281, No. 1.507,803, Special Publication No. 1977-
No. 4936, No. 53-12,375, JP-A No. 52-1
No. 10,618 and No. 52-109,925.

Furthermore, the silver halide emulsion used in the present invention can contain various known photographic additives. For example, R
e5earch Disclosure 17643.

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 light-sensitive material of the present invention can have any structure 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 agents used in the color developing solution of the present invention include those known and 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 salts or sulfur salts, since they are more stable than in the free state. Moreover, these compounds are generally used in color developing solution 11! About 0. II to a concentration of about 30 g, preferably color developer 11! About Ig to about 1
．． Use at a concentration of 5&.

Examples of aminophenol-based developers include O-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developers include N,
It is an N'-dialkyl-p-7-ethylenediamine-based compound, and the alkyl group and phenyl group may be substituted with any substituent. Among these, particularly useful compound examples include N,N/-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N/-dimethyl-p-7 22-diamine hydrochloride. Salt, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur! ? salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N'-
Examples include diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate, 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 that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkaline agents such as 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 developer is usually 7 or higher, most commonly about 10 to
It is about 13.

° In the present invention, after color development processing, processing is performed with a processing liquid having fixing ability, but if the processing liquid having fixing ability is a fixing liquid, bleaching processing is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt oxidizes metallic silver produced by development and converts it into silver halide. It has the effect of coloring the uncolored part of the coloring agent, 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 metal ions such as copper.

The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarmenic 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"l ethylenediamine-N-(β-oxyethyl) -N, N',
N'-triacetic acid ('4) Pyrene diamine tetraacetic acid [5] and trilotriacetic acid (6)? Glohexanediaminetetraacetic acid [7]
Iminodiacetic acid (8) Dihydrotetraxyethylglycine citric acid (or tartaric acid) (9) Ethyl ether diamine tetraacetic acid [1]
Glycol ether diamine tetraacetic acid (11)
Ethylenecinamine titrapropionic acid (12) Phenylenediaminetetraacetic acid (13) Ethylenediaminetetraacetic acid disodium salt (14) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt (16) Die) Lentriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl)-N, N', N'-)triacetic acid sodium salt (18) Propylenediaminetetraacetic 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. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Additionally, voice buffering agents such as borates, srs salts, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. .

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Potassium sulfite, ammonium bisulfite, bisulfite power 6
sulfites such as sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax.

Sodium hydroxide, potassium hydroxide, sodium carbonate,
It may contain one or more pH buffers consisting of various salts such as 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 nitrogen may be blown into the bleach-fix solution and the bleach-fix replenisher storage tank, or a suitable bleaching agent may be used. For example, harsh hydrogen, bromate, persulfate, etc. may be added as appropriate.

(Example) Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

[Example-1] The magenta coupler of the present invention and the comparative coupler as shown in Table 1 were each taken in an amount of 0.1 mol per mol of silver, and tricresyl phosphate in an amount of 1 times the weight of Kabuku and 3 Double the amount of ethyl acetate was heated to ω°C and completely dissolved. This solution was mixed with 1 part of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, Dapon f!s).
The mixture was mixed with 120 °C of a 5% gelatin aqueous solution containing 20 g of scraps, and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Thereafter, this dispersion was mixed into a green-sensitive silver iodobromide emulsion (silver iodide 6 mol%).
2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol=
1:1) 12 om was added and coated on a subbed transparent polyester paste and dried to prepare a sample. (
Coated silver amount 20? /Zoo cd) The sample thus obtained was subjected to wedge exposure according to a conventional method and then subjected to the following development treatment.Table 1 shows the results.

[Development process]

Color developer: 3 minutes and 15 seconds at ℃.Bleach solution: 4 minutes at ℃.Water wash for 4 minutes.
Audience ℃ 3 minutes 15 seconds fixation liquid feather ℃
Wash with water for 4 minutes ℃
Stable for 3 minutes and 15 seconds.Liquid 1 minute additional drying at 47℃ and 5℃ for 16 minutes (9) seconds.The composition of the treatment solution used in each treatment step is as follows.

[Color developer composition]

[Bleaching solution composition] [Fixing solution composition] [Stabilizing solution composition] 541 Table 1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of Capri density 0.1, and sample 11 using comparative coupler 1 was set as 100.

2) 30℃, 62%RH &: IIWIL, humidity controlled 0
After placing the sample in a sealed container containing 5 cc of 9% formalin aqueous solution for 3 days, color development is performed.

For comparison, a sample not treated with formalin is also developed.

3) The sample after the color development process was irradiated for 8 days in a xenon 7 ademeter, and the dye residual moisture % after the process at the initial density D = 1.0 was shown.

Comparative coupler 1 Comparative coupler 2 Comparative coupler 3 Comparative coupler 4 From Table 1, the couplers of the present invention have color development, formalin resistance,
It can be seen that the light resistance is improved in three respects compared to the comparative coupler.

[Example 2] Samples 11 to 19 in Example 1 were subjected to wedge exposure in the same manner, and then subjected to the following development treatment.

The results are shown in Table 2.

Specific sensitivity and light resistance were measured in the same manner as in Example 1.

[Development process]

Color development A℃ 3 minutes (capital) seconds Bleach fixing 33"C1 minute blade second tablet Kuni Shimi"! #I#! ]
I Dry at 4℃ for 3 minutes 1 to 8
0''C approx. 2 In the published treatment process, the composition of the treatment liquid used is as follows.

[Color developer]

[Bleach-fix solution] [Stabilizing solution] Table 2 [Example-3] A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide. was prepared.

The amounts added below are per 100.

(1) 20 mIP of gelatin, a blue-sensitive silver chlorobromide emulsion with a silver content of 5, and 8M9 of Y-coupler and 0.1"P of 2,5-di-t-octylhydroquinone dissolved in three layers. a layer containing a di-octyl 7-thaleate coupler solvent.

(2) An interlayer comprising L2q of gelatin, 0.5''9 of 2.5-dimyoctylhydroquinone, and 2wl9 of dibutyl 7-thaleate UV absorber solvent in which a UV absorbing uniformity of 4'I9 was dissolved.

(3) 18111F gelatin, silver content 4”9
green-sensitive silver chlorobromide emulsion, and a 5η M-coupler and 2
Antioxidant release of η and 2,5-di-t of 0.2'9
A layer containing 2,51 np dioctyl 7-thaleate coupler solvent in which octyl hydroquinone was dissolved.

(4) An intermediate layer containing the same composition as (2).

(5) 16η of gelatin, 4η of silver as a red-sensitive silver chlorobromide emulsion, and 3.5η of C-coupler and 0.
．． A layer containing 2,09 tricresyl phosphate 7ate coupler solvent in which 1η 2,5-di-t-octylhydroquinone was dissolved.

(6) Gelatin protective layer containing 9η gelatin.

Coating aids are added to each layer (1) to (6), and (
A gelatin crosslinking agent was added to layers 4) and (6).

(i) As the ultraviolet absorber in (4), UV absorbers with the following structure are used.
A mixture of UV-1 and UV-2 was used.

Di-t-pentylhydroquinone di-octyl ether was used as the antioxidant in (3).

The above multilayer photosensitive material was processed in the same manner as in Example-2.

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 in the same manner as in Example 1.

It is clear from Table 3 that the light fastness of the dye image of the coupler of the present invention is excellent, and it is also clear that it can be further improved by using an ultraviolet absorber.

~External radiation absorber UV-1 UV-2 C5Hll (t) Next Y-coupler -Coupler t=n3 L; f13 #r3 Table procedure amendment November 26, 1980 Patent application submitted on November 15, 1980 (12) 2. Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (1)
27) Roku Konishi Photo Industry Co., Ltd. 4, Agent 19
1. Residence: 1 Sakura-cho, Hino-shi, Tokyo, Vol. 6, Specification subject to amendment 7, Type engraving of the amended statement of contents (no change in content), -11-).

Claims (1)

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