JPS6364046A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide superior formation resistance to a photosensitive material by incorporating a specified pyrazoloazole type magenta coupler having a substd. alkyl group at the 6-position into the sensitive material. CONSTITUTION:A pyrazoloazole type magenta coupler having R2-C(-R1,-R3)-CH2- at the 6-position and represented by the formula is incorporated into a silver halide color photographic sensitive material. In the formula, R1 is alkyl, each of R2 and R3 is H or a substituent, each of Za-Zc is methine, substd. methine, substd. methine, methylene, =N- or -NH-, one of Za-Zb and Zb-Zc bonds is a double bond, the other is a single bond, Za-Zc form pyrazoloazole ring in combination, X is H or a group releasable by coupling and each of substituents represented by R2 and R3 may be halogen, alkyl, aryl, alkoxy, aryloxy, acyloxy, amino, cyano, nitro, hydroxy or carboxyl. Superior formalin resistance is provided to the sensitive material and the shelf stability of a dye 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, and more particularly to a silver halide color photographic light-sensitive material containing a novel magenta coupler.

[Prior art]

Couplers commonly used in silver halide color photographic materials (hereinafter referred to as color photographic materials) include yellow couplers made of closed ketomethylene compounds;
Magenta couplers made of pyrazolone compounds and pyrazoloazole compounds, cyan couplers made of phenol compounds and naphthol compounds, and the like are known.

Conventionally, pyrazolone compounds have been frequently used as magenta couplers. Known pyrazolone magenta couplers include U.S. Pat.
No. 519,429, JP-A-49-111631, 5
No. 7-35858, etc. However, The Theory of the Seven Autograph Processes (T
he theory of the photography
phic Process)y v Kumilan Publishing, 4th edition (1977), pp. 356-358, 77 In Chemical,
Published by CMC, Volume 14, No. 8, pp. 38-41,
Photographic Society of Japan 1985 Annual Conference (May 23-24, 1985, Private Institute Hall) Ill Abstracts, 108-
As described in No. 110, dyes formed from magenta couplers made of pyrazolone compounds have undesirable side absorption, and improvement thereof is desired.

As described in the above literature, the dye formed by the magenta coupler made of a pyrazoloazole compound has no side absorption.In addition to the above literature, the fact that this coupler is a good coupler is shown in U.S. Patent No. 3,725,06
No. 7, No. 3,758,309, No. 3,810,761
It is stated in the number etc.

However, even this excellent coupler does not have sufficient color development properties, and the dyes formed from the coupler also have insufficient storage stability, and improvements are desired.

[Purpose of the invention]

An object of the present invention is to provide a color photosensitive material containing a pyrazoloazole magenta coupler with improved color development. More specifically, it is an object of the present invention to provide a color light-sensitive material containing a pyrazoloazole magenta coupler that provides a dye with excellent formalin stain resistance and excellent storage stability.

[1lIIr& of the Invention] The above objects of the present invention have been achieved by a color photosensitive material containing a pyrazoloazole magenta coupler represented by the following general formula [I].

General formula (11 In the formula, R1 represents a furkyl group, R2 and R1 represent a hydrogen atom or a substituent (however, R2 and R1 are not both hydrogen atoms), Z a, Z b and Zc are Each represents methine, substituted methine, methylene, substituted methylene, =N- or -NH-, and one of the Za-zb bond and Zb-Zc bond is a double bond and the other is a single bond. Represents a hydrogen atom or a coupling-off group.

The present invention will be explained in more detail below.

The pyrazoloazole represented by the above general formula [I] is characterized by having an R2CCH2- group at the 6-position.

The furkyl group represented by R1 is preferably a straight chain, branched or cyclic alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, L-butyl group, octyl group. , dodecyl group, tetradecyl group, cyclopentyl group, cyclohexyl group, etc.

These alkyl groups may have a substituent, such as a halogen atom (e.g. fluorine, chlorine, bromine atom), a 7-aryl group (e.g. phenyl, naphthyl, 4-dodecyloxyphenyl group), an alkoxy group. (e.g. methoxy, ethoxy, 2-methoxyethoxy group), aryloxy group (e.g. phenoxy, 2,5-di-t-7-milphenoxy group), ami7 group (e.g. methylamino, diethyl 7mino, anilino group), 7 Silami7 group (e.g. acetamide, benzamide group), ureido group (e.g. methylureido, phenylureido group), sulfonamide group (e.g. methanesulfonamide, benzenesulfonamide group), carbamoyl group (e.g. methylcarbamoyl, diethylcarbamoyl, phenyl carbamoyl group)
, sulfamoyl group (e.g. methylsulfamoyl, diethylsulfamoyl, phenylsulfamoyl group),
Examples include a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl group), an alkylthio group (eg, methylthio, dodecylthio group), a 7-arylthio group (eg, phenylthio group), and the like.

Substituents represented by R1 and R3 include halogen atom, alkyl group, 7lyl group, alkoxy group, 7lyloxy group, ami7 group, 7syl7mino group, ureido group, sulfonamide group, carbamoyl group , sulfamoyl group,
The above R and R such as a sulfonyl group, an alkylthio group, and an arylthio group.

In addition to the groups specifically explained as substituents that have a hydroxyl group, carboxyl group, cyano group, nitro group, acyl group (e.g. 7 cetyl, benzoyl group),
Alfkidicarbonyl group (e.g. methoxycarbonyl,
octadecylcarbonyl group), heterocyclic groups (for example, 2-furyl, 2-chenyl, 2-pyriminoel, 2-benzothiazolyl group), and the like. Of these,
A halogen atom, an alkyl group, an alkoxy group, a furkylthio group, and a sulfonyl group are preferable.The group represented by R2 and R3 may further have a substituent, and examples thereof include the same substituents as explained for R7. .

Many pyrazoloazole nuclei are formed by the combination of Za, Zb and Zc, but among the couplers of the present invention that are attenuated by the general formula [I], preferred ones are represented by the following general formula (
It is represented by [], (IIl], (■), [V] or [■].

General formula (I[l) In general formulas (II) to (■), R, , R2, R.

and X each represent a group having the same meaning as general formula (1),
R1 and VRs each represent a hydrogen atom or a substituent, and examples of the substituent represented by R1 and R include the same groups as already described for R2 and R3.

The coupling-off group represented by , fluorine atom), alkoxy groups (e.g. ethoxy, pennoloxy groups), aryloxy groups (
For example, phenoxy, 4-nitrophenoxy groups), acyloxy groups (e.g. 7SeFxy, myrisFyloxy, benzoyloxy groups), alkylthio groups (e.g. methylthio, octylthio, benzylthio groups), arylthio groups (e.g. phenylthio, 2-propylene), F xy 5-octylphenylthio group), sulfone 7mido group, pyrazolyl group, tri7zolyl group, tetrazolyl group, and the like. Among these, halogen atoms are preferred.

Among the couplers of the present invention represented by general formulas (n) to (VI), more preferred are general formulas (■) and [■], and particularly preferred are couplers represented by general formula [■]. be.

Typical specific examples of the coupler represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.
I3 (17) CI
C, □H2S5CH2CCH2■ CHl R3X C2H.

C1゜82I CI2[125 C11) I35 C.I.

(25) CCH25O2C1llh7CH.

CH3C+5Ls r■.

(31) CI (CB, CH25O□c+J2tC
H3
Rko (40)
NHCOC, F.

(45) 5C82C) 1.0H (46) 5CH2COOH (47) 5CIJ33 (48) 0CHZCONIICLCLOCL(4
9) QC) 12cl(,SO,C)! .

(50) 0CH2CH2SCHCOO)1Cl2
) 12% 7 ethyl cetoacetate 101,5. Toluene 500m+2
and 28% methanol solution of sodium notchiller F [1
Add 50.5 g of the solvent, heat with stirring, and remove about 3.5 g of the solvent at normal pressure.
00 liters were distilled off. Furthermore, 700 l of toluene was added and the solvent was distilled off until the distillation temperature reached 110° (approximately 500 m
N), cooled to below 50°C, and added t-butylacetic acid chloride (b synthesized from t-butylacetic acid and thionyl chloride).
p127-131°C) 105. was dripped. 8
After stirring at 5°C for 1 hour, return to room temperature and 28% methanol solution of nasilium methylate! 50.5. was added and stirred for 1 hour. After standing overnight, the mixture was acidified with hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water three times and then concentrated under reduced pressure. Further distillation purification was carried out twice to obtain [1] at 67.4° (49
%) Obtained. bp 90~b Next [1] 40g
Add 200sZ of chloroform and cool to 10'C.
Ethanol (4,7N) 49.4-1 and 550 ml of 1-functional ethanol were added to the mixture and 31.35 g of sul7lyl chloride was added dropwise and 0 drops thereof were absorbed therein, and the mixture was heated under reflux for 6 hours.

The solvent was distilled off under reduced pressure, and 7 setsonitrile was added to the residue to remove the solid. Heat and wash with ethyl acetate to convert [2] into 4
0. (55%) obtained.

Next, (2) 35.3 g was suspended in 250 w1' of ethanol, and 45 g of hydranone hitrad was added dropwise while heating and refluxing. After 0 dropwise addition, refluxing was continued for another 2 hours, and then 1°2 of ice water was added.
I poured it into 1. After collecting the precipitated solid by filtration, washing with water, and drying, 7
c) 2) Recrystallized from ril to obtain 17.3 g (68
%)%Ta.

Next (3) 12.5. 30 ml of an aqueous solution containing 62.5 tl of ethyl acetate and 6.8 g of sodium acetate was added to suspend the solution, and 25 g of γ-(2-butoxy-5-t-octylbenzenesulfonyl)butyryl chloride was added thereto and the mixture was stirred at room temperature. Stir for hours. Water 1 was discarded, the ethyl acetate layer was washed with water, and then concentrated under reduced pressure. The residue was recrystallized from acetonitrile to obtain (4) 30.5FK (89%).

Next, 150@1 ethyl acetate and 11.5 g of thionyl chloride were added to 30 g of [4], and the mixture was heated under reflux for 2 hours. The mixture was cooled to room temperature, water was added, and the ethyl acetate layer was extracted. 940ml of an aqueous solution of 9.7g of potassium hydrogen carbonate dissolved in the ethyl acetate layer
7 was added, and the mixture was heated under reflux for 2 hours. The aqueous layer was discarded, and the ethyl acetate layer was washed with water, concentrated under reduced pressure, and the residue was recrystallized from 7cetonitrile to obtain 22.7g (78%) of [5].

Next, 10 mf of water and 110 mN of concentrated water were added to 20 g of (5) and heated under reflux for 5 hours. The reaction mixture was poured into 500 mZ of ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and concentrated under reduced pressure to obtain 17.5 g (97%) of [6].

This product was used in the next reaction without purification.

Next (6) 15. was dissolved in 75 liters of ethyl acetate, and N
- 3.7 g of chlorosuccinimide was added and stirred at room temperature for 1 hour. 100 mZ of water was added to this to extract the ethyl acetate layer, which was washed with water and then concentrated under reduced pressure. The residue was recrystallized from 7 ml of chloride to give the exemplified coupler (24
) to 14. Og (88%) was obtained.

Elemental analysis value (C3°H,, CZN, 0.S) Theoretical value (%
) C:62,21 H:8.18 N:9,
8F S: 5.54 Actual value (%) C: 62.0
8 H: 8.16 N: 9,55 S: 5,71%MR
The spectrum and FD mass spectrum are also 3-13-<2-butoxy-5-t-octylphenylsulfonyl)propyl)-6-neopentyl-7-chloro-IH-pyrazolo(5,1-e)-1,2,4 -) Supported the structure of lyazole.

The couplers of the invention are typically 1x1 per mole of silver halide.
0-Comole 1 mol, preferably lXl 0-” mol to 8 mol
It can be used in the range of X10-' moles.

Further, the coupler of the present invention can be used in combination with other types of magenta couplers as long as the effects of the present invention are not impaired.

The silver halide emulsions used in the present invention include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any used can be used.

The silver halide grains may have a uniform silver halide distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of 1loo1 side to 1llll1 side can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The grain size of silver halide grains is 0.05 to 30
μ, preferably 0.1 to 20 μ can be used.

Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. ) may be used alone or in combination of several kinds, or a polydisperse emulsion and a monodisperse emulsion may be mixed.

The coupler used in the present invention includes a colored coupler having a color correction effect and a development inhibitor, a development accelerator, a bleach accelerator, etc. by coupling with an oxidized form of a developing agent.
7. Photographically useful agents such as developing agents, silver lodenide solvents, toning agents, hardeners, capri agents, anti-capri agents, chemical sensitizers, spectral sensitizers, and desensitizers. Among these compounds, so-called DIR compounds which release a development inhibitor during development and improve image sharpness and image graininess may be used.

The so-called DIR compounds used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the molecule in the base circle released by the coupling reaction. These include timing DIR compounds that bind in such a way that the inhibitor is released by internal nucleophilic reactions, intramolecular electron transfer reactions, etc. Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow coupler that may be used in the present invention, known acyl 7cetanilide couplers can be preferably used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous.

As cyan couplers that may be used in the present invention, phenol or 7-tole couplers are generally used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color anti-capri agent can be used to prevent the color from being noticeable.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of RD17843.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain an ultraviolet absorber to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent deterioration of images due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

The present invention can be preferably applied to color negative films, color papers, color reversal films, and the like.

Color film, color paper, and color reversal film generally consist of a blue-sensitive, green-sensitive, or red-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer.
The present invention is not limited in any way to the arrangement of these layers on the support.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Color photographic processing is performed, and color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Instead of the processing steps used above, a one-bath bleach-fixing solution can be used to carry out the bleach-fixing processing step, or a one-bath developing, bleach-fixing solution that can perform color development, bleaching, and fixing in one process can be used. It is also possible to perform a monobath treatment process using

〔Example〕

Next, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A magenta coupler of the present invention and a comparative coupler as shown in Table 1 were each taken at 0.1 mol per mol of silver, and tricresyl phosphate was added in an amount of 1 times the weight of the coupler and tricresyl phosphate was added in an amount of 3 times the weight of the coupler. of ethyl acetate was added and heated to 60°C to completely dissolve. This solution was mixed with Flukanol B (alkylna 7).
5% aqueous solution of Talensphonate (manufactured by DuPont) 120
1,200 mj of 5% gelatin aqueous solution containing s/! Then, this dispersion was mixed with a green-sensitive silver iodobromide emulsion (containing 6 mol % of silver iodide) 4K.

and a 2% solution of 1,2-bis(vinylsulfonyl)ethane (water:methanol=1:1) as a hardening agent.
Samples 1 to 8 were prepared by adding 120 mf and coating and drying on a transparent undercoated polyester base (coated silver 1
1120IIIg/100100e.

The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. The results are shown in Table 1.

[Development process] Color development 38℃ 3 minutes 15 seconds bleaching
White 38℃ 4 minutes 2
Wash with water for 0 seconds at 38℃
Fixed for 3 minutes and 15 seconds at 38℃
Wash with water for 4 minutes and 20 seconds 38
℃ 3 minutes 15 seconds stabilization 38℃
Drying for 1 minute and 30 seconds at 47° C.±5° C. for 16 minutes and 30 seconds In each treatment step, the composition of the treatment liquid used was as follows.

[Color developer composition]

Potassium carbonate 30. Ofsodium bicarbonate 2.5gPotassium sulfite s,og Potassium iodide 1.3゜Potassium iodide
2.0+sg Hydroxylamine sulfate 2.5g F chloride
0.6g sodium ethylenetriaminepentaacetate 2.5g 3-methyl-4-7minor N-ethyl-N-(β-hydroxyethyl)aniline sulfate
4.8g potassium hydroxide
Add 1.2 g of water to bring the total volume to 11, and adjust the pH to 10.06 using potassium hydroxide or 20% sulfuric acid.

[Bleach solution composition]

Iron ammonium salt of ethylenediaminetetraacetate 100.0g Iron ammonium salt of ethylenediaminetetraacetate 10.0g Seven ammonium bromide 150. Og ice vinegar @ 40. Sodium Owl 10.0゜ Add water to make 11, and adjust to pH 3 using 7 ml of water or glacial acetic acid.
, 5 to set W4.

[Settlement 8! Ammonium thiosulfate 180.0g Anhydrous sodium sulfite 12.0g Sodium metabisulfite 2.5g Ethylenecyaminetetravinegar R2 sodium trihum o, sg Sodium carbonate
Add 10.0g water to make 11.

[Stabilizing liquid composition]

Formalin (37% aqueous solution) Z, 0
I11 Funigtsukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 5
．． Table 1 1> The specific sensitivity is 100 for Sample 1 using Comparative Coupler 1 with the number of teeth at Exposure 1 which gives a density of 0.19 in the overlapping density.

2) After placing the sample in a sealed container for 3 days in which 6 liters of 0.9% formalin aqueous solution, whose temperature and humidity were controlled to 32°C and 62°C, was subjected to color development. For comparison, a sample not treated with formalin is also developed.

Less than or equal to e -+7' Comparative coupler 1 Comparative coupler 2 C・0H21 Comparative coupler 3 As is clear from the table, the sample according to the present invention has a high maximum concentration without a decrease in sensitivity, and has excellent formalin 1 property and has a good shelf life. was confirmed to be in good condition.

Example 2 Samples 1 to 8 in Example 1 were exposed to 7 squares in the same manner, and then subjected to the following development treatment. The results are shown in Table-2.

[Development process]

Color development 38℃ 3 minutes 30 seconds bleach fixing
Stabilization treatment at 33°C for 1 minute and 30 seconds 25~
30°C for 3 minutes (or washing with water may be used) Drying 75-80°C for about 2 minutes In each treatment step, the composition of the treatment liquid used is as follows.

[Color developer]

Bennol Alcohol 15-1 Ethylene Glyfur 15-1 Potassium Sulfite 2.0g Potassium Bromide 067g Potassium Chloride
0.2g potassium carbonate
30.0゜Pyroxylamine sulfate
3.0゜Ho 17 phosphorus (TPPS)
2.5[13-Methyl-4-amino-N-ethyl-N-(β-notanesulfone7midoethyl)7niline sulfate 5.
5g Fluorescent brightener (4,4'-diaminostilpentesulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total volume to 11, and adjust the pH to 1.20.

[Bleach-fix solution]

Ethylenecyaminetetraacetic acid ferric heptadium dihydrate 60. Og ethylenediaminetetraacetic acid 3.08 thiosulfate 7
Ammonium (70% soluble fi) 100.0mff1
Ammonium sulfite (40% dissolved a) 27.
5 orders, 1 ice vinegar! l!
10.0 Proverbs! Adjust p) to 14 to 17.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 11.

[Stabilizing liquid]

5-chloro-2-methyl-4-isothiazolin-3-one 1.Og
Ethylene glycol 10.0g! I
c-2 1) The specific sensitivity is 100% for sample 2-1 using the comparison coupler at the number of teeth at the exposure amount that gives the density +0.1181 degrees.
And so.

2) The sample after color development treatment was irradiated with a xenon 7 ademeter for 5 days, and when the initial density D = 1.0, -/ As is clear from the table, the sample according to the present invention showed no decrease in sensitivity (maximum It was confirmed that the density was high, the light fastness was excellent, the magenta image did not fade, and the storage stability was good.

Example 3 A multilayer color photosensitive material was prepared by sequentially coating the following layers on polyethylene resin coated paper containing 7-natase type titanium oxide. Incidentally, the amount added in the light-sensitive material is the amount per 100 c.

(1) 20 g of gelatin, 5B silver chloride emulsion (containing 80 mole percent silver bromide), and 8 g
yellow coupler bulk and 0.1B of 2,5-note
Layer (2) containing dioctyl 7-talate of octylhydroquinone, 311 & 12 g of gelatin, 0.5 g of 2,5-
An interlayer comprising not-t-octylhydroquinone and 4 t-g of ultraviolet absorber and 82 t-g of butyl 7-talate.

(3) 18-8 of gelatin, 4 mg of green-sensitive silver chlorobromide emulsion (containing 70 mole percent silver bromide) as silver, and 5 oz of magenta coupler 8 and 2 mg of antioxidants 1 and 0. A layer containing 2 mg of 2,5-not-t-octylhydroquinone, 2.5 mg of dioctyl 7-talate.

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

(5) 16 mg of gelatin, 4-g silver of erythrocytic silver emulsion (containing 70 mole percent silver bromide), and 3°5B of cyan coupler 8 and 0.1 g of 2, 5
- a layer containing t-octylhydroquinone, 2.0 t-g of tricrenophosphate.

(Protective layer containing 639 mg of gelatin.

Book (2)? As the ultraviolet absorber (4), tlV-1 and UV-2 having the following structures were mixed (mixing ratio 1:1) and used.

*Nort-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 yellow coupler, magenta coupler, and cyan coupler used in each layer and the results.

The magenta density of each sample was measured after exposure to white light.

Specific sensitivity and light resistance were measured in the same manner as in Example-2.

From the results shown in Table 3, it is clear that the light fastness of the color 'lA 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.

Ultraviolet absorber V-1 H V-2 H CsHz(t) Yellow coupler Y-1 I I Cyan coupler I Example-4 Each layer having the composition shown below was supported in sequence on a tri-7 cetyl cellulose film support. A multilayer color photosensitive material 19 was prepared by coating from the body side. Incidentally, the amount added in the silver halide photographic light-sensitive material is shown per IC unless otherwise specified, and the amounts of silver halide and colloidal silver are shown in terms of silver.

1st layer: Halic acid prevention layer (HC) Gelatin layer containing black colloidal silver.

2nd Layer: Intermediate Layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer: Low sensitivity red-sensitive silver halide emulsion layer (RL) Average grain size (r) 0.30μ ring, monodisperse emulsion consisting of 8 girls containing 8g and 16 mol% (emulsion I)--Single silver coating side [,8 g/2 sensitizing dye 1 ---- 6 x 10-' mol sensitizing dye n - per mole of silver
---- 1 per mole of silver. OX 10-'Morsian coupler (C-S) ----1*0.0 per 1 mole
6 mol colored cyan coupler (CC-1)---0.003 mol DIR compound (D-1) for 1 mol silver---0.0015 mol DIR compound (D-1) for 1 mol silver -2) ----0.002 mol per mol of silver 4th layer: Highly sensitive red-sensitive silver halide emulsion layer (RH) Average grain size (r) 0.5 μl, ^, 17.0 mol Monodispersed emulsion (emulsion ■) consisting of 8 gBrl containing % - coating weight of 11 silver 1.3 g/2 sensitizing dye 1 ----- 3 x 10-' mol sensitizing dye ■ for 1 mole of silver - ---- 1.0 per mole of silver. OX 10-'Morsian coupler (C-5) ----0.02 per mole of silver
Molar colored cyan coupler (CC-1) -1-0.0015 mol per 1 mol of silver DIR compound (D-2) ----0.001 mol per 11 mol 5th layer: Intermediate layer ( 1,L,) Gelatin layer with the same composition as the second layer.

6th layer: Low sensitivity green-sensitive silver halide emulsion 7! ! I (G
L) Emulsion - 1-m-silver coating ji 1.5 g/'in 2 sensitizing dye m --- 1- 2,5X 10-' mol sensitizing dye y per 1 mol silver
----- 1,2X 10-' mole magenta coupler (M-1) per mole of silver ---0.0 per mole of silver
50 mol colored magenta coupler (CM-1>---0.009 mol DIR compound CD-1 per mol silver) ----0.0010 mol DIR compound (D-3 per mol silver) ) ------0.0030 mol per 1 mol of fIA 7th layer: Highly sensitive green-sensitive silver halide emulsion layer (Ct+) Emulsion-n-m- Silver coating 11.4 g/
m2 sensitizing dye m ---1- 1,5X 10-5 mol sensitizing dye N per 1 mol silver
------- 1 for 491 moles. OX 10-' mole magenta coupler (M-1) ----0 per mole of silver
．． 020 mol Colored magenta coupler (CM-1)---0.002 mol per mol of silver DIR compound (D-3) -1---0.0010 mol per mol of silver 8th layer :Yellow filter: a yellow gelatin layer containing colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer: Low-speed blue-sensitive silver halide emulsion layer <BL) Monodispersed emulsion (emulsion ■) consisting of 8 gBrl containing average grain size (n 0.48 μm, ^g 16.0 mol%) Silver coating amount 0.9 g /Export 2 Sensitizing Dye V ------ 1.3X 10-S mole per silver silver Coupler (Y-3) ---1-0.
29 mol 10th layer: Highly sensitive blue-sensitive silver halide emulsion layer (BH
) Average grain size (r) 0.8 μ theory, monodisperse emulsion consisting of 8 gBrl containing 115 mol % of heg (emulsion ■) Silver coating amount 0.5 g/m' Sensitizing dye V ----- Silver 1 mol For 1. OX 10-S mole yellow coupler (Y-3) ----0.0% per mole of silver.
08 mol DIR compound (D-2) ---- 0.0015 mol per mol of silver 11th layer: 1st protective layer (Pro 1) Silver iodobromide (^g
ll %, average particle size (1) 0.7μ theory> -----1 Silver coating amount 0.5. /ugly 2 ultraviolet absorber uv-1, UV
-2 (mixing ratio 1:1) gelatin layer.

12th layer: 2nd protective layer (Pro-2) Polymethyl methacrylate particles (average diameter 1.5 μm) and formalin scavenger (HS)
In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each gelatin interlayer including -1).

Furthermore, Sample 20 was prepared in the same manner as Sample 19 except that M-1 of layers 6 and 7 in Sample 51 was changed to the coupler (2) of the present invention.

The compounds contained in each layer of each sample are as follows.

Sensitizing dye ■: Anhydro 5.5'-Nochloro 9-
Ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-4,5,4'.

5'-dibezothi7 carpocyanine hydroxide sensitizing dye ■: Anhydro 5.5'-7 phenyl-9
-Ethyl-3,3'-c(3-sulfopropyl)oxycarbocyanine hydroxide sensitizing dye■: Anhydro9-ethyl3,3'-no(3-sulfopropyl)-5,6,5',6 '-Nobenzooxalpocyanine hydroxide sensitizing dye ■: Anhydro 3,3'-no(3-sulfopropyl)-4,5-benzo-5'-methoC-1 R H H M-1 CI CI l This Samples 19 and 20 thus obtained were subjected to wedge exposure using white light, and then subjected to the following development treatment.

[Development processing process] (38℃) Color development phenomenon 3 minutes 15 seconds bleaching
white 6 minutes 30
Second wash
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color development 1p, liquid] 4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4,25° hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5@potassium hydroxide 1.0° Add water to make 11.

[Bleach solution]

Ethylenedi7minetetraacetic acid iron ammonium salt 100. OB Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0° Glacial acetic acid
Add 10.0mf water and 1
1 and adjust the pH to 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 11, and adjust to pus, o using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5 liters (Konishiroku Photo Industry Co., Ltd.) Add 7.5 mN water and 1
Set to 1.

For these samples, formalin resistance of magenta images was determined in the same manner as in Example 1, in which formalin resistance was determined. The results obtained are shown in Table-4.

Table 4 As is clear from the table, by using the magenta coupler of the present invention, a photosensitive material with extremely good formalin resistance could be obtained.

Applicant: Konishiroku Photo Industry Co., Ltd. Procedural amendment April 6, 1986

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a pyrazoloazole magenta coupler represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an alkyl group, R_2 and R_
3 represents a hydrogen atom or a substituent (however, R_2 and R
_3 cannot both be hydrogen atoms). Za, Zb and Zc each represent methine, substituted methine, methylene, substituted methylene, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. It is a combination. X represents a hydrogen atom or a coupling-off group. ]