JPS6055343A - Color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the sensitivity, developed color density and resistance to formaldehyde by incorporating a specified magenta coupler into a silver halide emulsion layer on a support. CONSTITUTION:A magenta coupler represented by the formula is incorporated into a silver halide emulsion layer on a support to obtain a photosensitive material having high sensitivity and high resistance to formaldehyde and developing color at high density. In the formula, R1 is alkyl or aryl; R2 is a univalent group; R3 is alkylene. Y is halogen, hydroxy or alkyl; Z is a group which can be eliminated by a coupling reaction with the oxidized product of a color developing agent; l is an integer of 1-5; m is an integer of 0-4; and n is an integer of 1-5.

Description

Detailed Description of the Invention ■1 Background of the Invention Technical Field> The present invention provides a silver halide color photograph that exhibits a high coloring basis with lvi sensitivity and further improves storage stability and provides a maze/liquid image. Regarding Kanbujinekoma.

<Prior art and its problems> Generally, in silver halide color photographic light-sensitive materials, exposed silver halide grains are treated with an aromatic primary amine color developing agent, and the color developing agent produced at this time is A dye image is created by coupling the oxidized form of the main drug with couplers that form yellow, magenta, and cyan dyes.
I can be a samurai.

The coupler that has been practically used to form the magenta dye is the pyrazolone type magenta coupler, but it has low maximum color density and sensitivity, has undesirable side absorption, and has poor storage stability, especially formalin resistance. There were drawbacks such as poor color tone change and significant deterioration in color development.

Many proposals have been made in the past to improve these drawbacks. For example, in Japanese Patent Publication No. 48-30'895, IH-pyrazolo [
Although magenta couplers of the 3,2-C]-s-triazole type have been disclosed, there has been little improvement in maximum color density and sensitivity, and in formalin capping.

Further, Japanese Patent Publication No. 16058/1983 discloses a screw type pyrazolone type magenta cag 2-.

Although this coupler shows some improvement in sensitivity and formalin resistance, the reduction in maximum color production is insufficient. Furthermore, JP-A-56-135) 141 1c discloses an IH-pyrazolo[3,2-C]-5-) lyazole magenta coupler in which the 1st position is substituted with the active point of a compound having an active methylene group. There is. Although this coupler has somewhat improved formalin resistance, its maximum color density and sensitivity U are insufficient.

Furthermore, in JP-A No. 58-42045, a ballast group having a hydroxyphenylene sulfonyl group at the K terminal is disclosed as a ballast group in sonograms for the purpose of improving the maximum color density. It is.

(9) Purpose of the Invention The first object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits high maximum color density and high J g'Jy in a magenta color layer and excellent formalin resistance. It is in. A second object of the present invention is to provide a silver halide color photographic material that does not have undesirable sub-absorption in the magenta coloring layer. Third aspect of the present invention
The object of the present invention is to provide a silver halide color photographic light-sensitive material with excellent fractional stability of magenta couplers for photography.

A fourth object of the present invention is to provide a silver halide color photographic material that provides rare dye images.

(2) Structure of the Invention The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer has the following general formula [2]
This was accomplished by using a silver halide color photographic light-sensitive material containing at least one magenta coupler represented by the following formula.

General formula CI) In the formula, R, Iri represents an alkyl group or an aryl group, Rt represents a monovalent group, Rs represents an alkylene group, Y represents a halogen atom, a hydroxy group or an alkyl group, and 2 represents a color-forming Represents a group that can be separated by a coupling reaction with the oxidized form of the current iron main drug, and l! represents an integer from 1 to 5, m represents an integer from 0 to 4, and n represents an integer from 0 to 5, respectively.

(2) Detailed Description of the Invention In the general formula [I], R1 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 alkyl groups,
Examples include methyl group, ethyl group, ethoxyethyl group, and t-butyl group.

The aryl group represented by R1 is preferably a phenyl group, and this phenyl group may have a substituent, such as p-methoxyphenyl group, m-chlorophenyl M,
p-(t)-butylphenyl/L' group, etc.

R, u, halogen atom (chloro group, etc.), alkoxy group (
It represents a monovalent group such as a methoxy group, t-butoquino group, etc.), an alkyl group (methyl group, ethyl group, methoxyethyl group, be/zyl group, etc.), a nitro group, a cyan group, etc.

R3 represents an alkylene group, for example, a methylene group, 1
．． 1-ethylene, 4.1.3-propylene group, 1.1-
Examples include alkylene groups such as nonylene group, 1,1-dodecylene group, and 111-tridecylene group.

The atom represented by Y is preferably a chloro atom, and the alkyl group represented by Y is preferably an alkyl group having 1 to 1 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, etc. , t-amyl group, t-octyl group, n-dodecyl group, n-pentadecyl group, and the like.

The group represented by 2 which can be separated by a coupling reaction with an oxidized product of a color developing agent means a group conventionally known as a so-called split-off group of a two-dimensional coupler, and does not contain a hydrogen atom. Specifically, the no.rogen atom (
For example, chloro atom, fluorine atom, etc.), aryloxy group (for example, phenoxy group, p-methoxyphenoxy group, p
-butanesulfonamidophenoxy group 1. P-te
rt-butylcarboamidophenoxy group, etc.), arylthio group (e.g. phenylthio group), heteroarthio group (e.g. 1-ethyltetrazole-5-thioyl group), preferably a halogen atom, particularly preferably a chloro atom De Al.

l represents an integer from 1 to 5, particularly preferably an integer from 1 to 3. m represents an integer from 0 to 4, particularly preferably 0. nUO represents an integer of 5, preferably an integer of 1 to 3. When n is 2 or more, Y is the same but different groups exhibits a ballast group sufficient to impair the diffusion resistance of the photographic magenta clouder represented by the general formula, and when Y is an alkyl group, The total number of carbon atoms of the alkylene group of R3 and the alkyl group of Y is preferably from 8 to 8, particularly preferably from 12 to 5. When n is O, an integer from 1 to 3, and Y is selected from a halogen atom and a hydroxy group, the alkylene group represented by R3 preferably has 8 to 8 carbon atoms.

Typical specific examples of the magenta cobbler of the present invention are described below, but the present invention is not limited thereto.

The magenta coupler of the present invention can be easily synthesized by conventionally known methods. Below are general examples of synthesis routes.Next, specific synthesis examples are shown.

Synthesis example 1. Exemplary coupler (Synthetic acetic acid 15 of M-21 (
Dissolve 4.59 n of anhydrous sodium acetate in lcc, and add 6.59 n of anhydrous sodium acetate at room temperature.
12.7 g of -methyl-3-(3-(p-aminophenyl)-glovyl]-IH-pyrazole[3°2-c]-o-)riazole was added, and while stirring, γ-(2,4- 18.6 g of butanoyl chloride was added little by little. After stirring for 8 hours, the reaction solution was added to water. Oil formation. After extraction with ethyl acetate and washing with water, the oil layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using a silica gel column and crystallized using ethyl acetate and n-hexane to obtain 15.3 g of white powder.

11.1 g of the obtained white powder was mixed with 110 ca of chloroform.
Add 3.0 g of sulfuryl chloride to 30 ml of chloroform and cool to 10°C ± 3°C using ice water.
The acid solution was slowly added dropwise. After dropping for 1 hour, the mixture was reacted again at the same temperature for 1 hour. The reaction solution was added to water, washed with water, the chloroform layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography and then recrystallized from acetonitrile.

4.8 g of white powder with mP 148-149°C was obtained. ◎Structure was determined using Oka and MASS.

Synthesis Example 21 Synthesis of Exemplary Coupler (M-7) 6-
Methyl-3-(3-(P-aminophenyl)propyl)
-IH-pyrazole[3,2-c]-s-triazole 12.711 was added, and while stirring, 25.0 g of α-(4-acetyloxy-3-tθrtbutylphenoxy)tetradecanoyl chloride was added in small portions. Added. After stirring for 6 hours, the reaction solution was added to water. Oil formation.

After extraction with ethyl acetate and washing with water, the oil layer was completely separated, dried over anhydrous magnesium sulfate, and the m-solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography to obtain a white oil at 24.5 F.

White oil 20II'f: Dissolved in 200 CC of chloroform, cooled with ice water to 10 °C and 3 °C, and 4.5 g of sulfuryl chloride in chloroform and 45 cc of acid solution were added dropwise over 1 hour. After further reaction for 1 hour at the same temperature,
Add water, wash, and separate the chloroform layer.

After drying using anhydrous magnesium sulfate, the m medium was distilled off.

The residue was treated with silica gel column chromatography to obtain a white oil.
．． I got 5g.

White oil 7.1, li' with ethanol 30cc, x
Add to 30cc of water and 1.2JFII solution of caustic soda at 40°C.
The soil was heated to 5°C for 1 hour. The reaction solution was made c, uc7 acidic. Oil formation. After extraction with ethyl acetate and washing with water,
The oil layer was separated and dried using anhydrous magnesium sulfate.

Thereafter, the m medium was distilled off under reduced pressure. The residue was purified using silica gel column chromatography and then re-crystallized using acetonitrile.

mp', 63-65°C white powder 3.61%. The structure was determined using NMR and MASS.

Silver halogenide color photographic materials prepared using the above-mentioned couplers according to the present invention (hereinafter referred to as couplers of the present invention) may contain conventionally used dye-forming couplers.

As a conventionally used yellow dye-forming coupler, a known open-chain ketomethylene type Kagler gold can be used. Among these, pivaloylacetanilide couplers or benzoylacetanilide couplers are useful. Specific examples of yellow dye-forming couplers that can be used include U.S. Pat. No. 2,875.
No. 057, British Patent No. 1,077.874, US Patent No. 3
, 408, 194, JP-A-50-123342, JP-A-50-87650, JP-A-54-133329, JP-A-46-19031, JP-A-48-29432, JP-A-4
No. 8-66834, No. 48-66835, No. 48-9
No. 4432, No. 5 o-28834, No. 54-99
No. 433, No. 55-70841, No. 56-74249
No., Special Publication No. 45-19956, Japanese Patent Publication No. 1026-1973
No. 36, No. 56-87041, etc.

As cyan dye-forming couplers, phenolic compounds,
Naphthol compounds and the like can be used. Specific examples include U.S. Patent Nos. 2,369.929 and 2,4.
No. 74,293, No. 2,772,162, No. 2,89
No. 5.826, British Patent 1. Q38,331, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 47-21139, U.S. Pat. 124.39
No. 6, No. 4,333,999, JP-A-55-2109
No. 4, No. 50-112038, No. 50-1 1 74
No. 22, No. 52-18315, No. 54-3.1523
No. 0, No. 55-163537, No. 57-136650
No. 57-155538, No. 57-204545, No. 55-32071, No. 55-108662, No. 56-1938, No. 56-271.47, No. 56-
Examples include those described in No. 80045 and No. 56-104333.

As the magenta pigment-forming graph, the couplers of the present invention may be used alone or in combination of two or more, and in addition, conventionally known pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, hilazolinopenzimidazole compounds may be used. Compounds, pyrazolotriazole compounds, etc. may be used in combination as appropriate. However, at least one is a coupler of the present invention.

In using the magenta couplers of the present invention, the methods used for conventional magenta dye-forming couplers are similarly applicable. Typically, the magenta coupler of the present invention is blended into a silver halide emulsion, and this emulsion is coated on a base to form a silver halide color photographic light-sensitive material.

This silver halide color photographic light-sensitive material may be monochromatic or multicolored. In the multicolor case, the magenta couplers of the invention are usually included in green-sensitive emulsions, but in non-sensitized f
It may be contained in an emulsion layer having VC sensitivity in the three primary color regions of the spectrum other than green.

Each structural unit forming a dye image in the present invention is
It consists of a single-pore agent layer or a multilayer γL agent layer that is photosensitive to a certain region of the spectrum.

The layers required for silver halide color photographic materials, including the stroke-forming unit layers described above, can be arranged in various orders as known in the art.

A typical multicolor silver halide color photographic material contains at least one cyan dye image-forming building block consisting of at least one red-sensitive silver halide γL'AIJ 1m ringing at least one cyan dye-forming coupler. a magenta color-finished image forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler (at least one of the magenta dye-forming couplers is a magenta coupler of the invention); Yellow color consisting of at least one blue-sensitive silver halide emulsion layer with one yellow color forming coupler X ll81i l!
It consists of a forming structural unit supported on a support.

This photographic material has additional layers, such as a filter layer,
It can have an intermediate layer, a protective layer, and an undercoat layer.

In order to incorporate the magenta coupler of the present invention and each coupler according to the present invention into a silver halide light-sensitive material, conventionally known methods may be followed. For example, after dissolving the magenta coupler of the present invention or each coupler according to the present invention in a mixture of a known high-boiling solvent and a low-boiling reagent such as butyl acetate or butyl gropionate, gelatin water core containing a surfactant is added. The silver halide emulsion used in the present invention can be prepared by mixing it with a liquid and emulsifying it using a high-speed rotary mixer, a colloid mill, or an ultrasonic disperser, and then adding it to silver halide.

Known high-boiling point solvents include phthalic acid esters (e.g. dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (tricresyl phos7.7ate, trioctyl phosphate, etc.), N-substituted acid amides (N , N
-diethyllaurinamide, etc.) are representative.

When added to the magenta coupler of the present invention and each coupler according to the present invention and the silver halide γL agent, it is usually about 0.01 to 2 mol per mol of silver halide, preferably f.
It is added in a range of 0.03 to 0.5 mol.

The silver halogenide used in the silver halogenide emulsion used in the present invention is commonly used, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiobromide, etc.・Includes anything used in silver halide emulsions.

The silver halogenide emulsion constituting the silver halogenide emulsion layer according to the present invention can be produced by various manufacturing methods including the usual manufacturing method.
For example, a method such as that described in Japanese Patent Publication No. 7772/1983 is used, in which an emulsion of silver salt grains is formed which consists of at least a portion of silver salt having a solubility greater than that of silver bromide, and then at least a portion of the grains are A method for producing a so-called conversion emulsion, such as converting silver bromide or silver iodobromide, or u o
The emulsion can be prepared by any manufacturing method such as the method of manufacturing a Lippmann emulsion consisting of finely divided silver halide having an average grain size of , iμ or less. Furthermore, the silver halide emulsions of the present invention may contain sulfur sensitizers such as arylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts. , polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzthiazole methyl chloride, etc., or water-centered salts such as ruthenium, rhodium, iridium, etc. Chemical sensitization can be carried out using sensitizers such as ammonium chlorovaladate, potassium chloroaurate, and sodium chloroparadite alone or in combination as appropriate.

Further, the silver halide emulsion used in the present invention can contain various known photographic additives. for example"
Research Disclosure” December 1978, A
17643.

The silver halide used in the present invention is spectral sensitized by selecting an appropriate sensitizing dye to impart photosensitivity to the required wavelength range. Various types of spectral sensitizing dyes can be used, and these can be used alone or in combination of two or more types.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
No. 0,378, No. 2,442,710, No. 2.454
．． Soanine dyes, merocyanine dyes, and fc as described in No. 620 and No. 2,776.280 are representative examples of complex cyanine dyes.

The support according to the present invention may be appropriately selected from conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. depending on the intended use of the photographic material. These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

(2) Specific Utilization of the Invention The silver halide color photographic material of the present invention thus constructed can be subjected to various photographic processing methods for color development treatment after exposure. A preferable color developing solution used in the present invention is an aromatic primary amine color developing solution (based on a herbal medicine as a main component).

A typical example of this color developing agent is a p-)unilene diamine type, such as diethyl-p-
Phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dogsylamino)- Toluene, 2-amino-5-(N-ethyl-N-
β-methanesulfonamidoethyl)amine toluene sulfur t
R salt, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-
β-hydroxyethylamino)aniline, 2-amino-
Examples include 5-(N-ethyl-β-methoxyethyl)amine toluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with a black and white developing agent such as hydroquinone.

Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and various additives such as alkali metal halides such as potassium bromide, or @It may contain a regulator such as hydrazine acid.

The silver halogenide color photographic light-sensitive material of the present invention may contain the above-mentioned color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. The color-forming agent P-V cursor is a compound that can form all the color-forming agents under alkaline conditions, including a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, Examples include phosphoric acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 342.599, No. 2,507,114, No. 2,6
No. 95,234, No. 3,719,492, British Patent 8
No. 03,783, JP-A-53-135628, JP-A No. 54
-79035, Research Disclosure Magazine 15
．． No. 159, No. 12,146, and No. 13.924.

These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. Although this amount varies considerably depending on the type of photosensitive material, it is generally photosensitive silver halide 1
Between 0.1 and 5 mol per mole, preferably 0.5
It is used in a range of mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. In order to incorporate the compound "4/B" into a photographic light-sensitive material, water, methanol, ethanol,
It can also be dissolved in a suitable solvent such as acetone and added.
It can also be added as an emulsified dispersion using a high-boiling point organic hexasol such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate, and can be added by impregnating it into a latex polymer as described in Research Disclosure No. 14850. It can also be added.

The silver halide color photographic light-sensitive material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and water washing after color development processing.

Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (), cobalt (cobalt plate), tin (n),
In particular, complex salts of these polyvalent metal cations and organic acids,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, N
-Aminopolycarboxylic acids such as hydroxyethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. alone or in appropriate combinations. used in

(2) Specific Examples of the Invention The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Example-1] The magenta power dollar 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 and tricresyl phosphate of 1 times the coupler weight were taken. Three times the volume of ethyl acetate was added and the mixture was heated to ω°C to complete the atrium. This solution was mixed with 120% water bath solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
It was mixed with 5% gelatin aqueous acid solution containing m1k and emulsified and dispersed using an ultrasonic dispersion machine to obtain an emulsion. Afterwards,
This dispersion was added at 4:00 to a green-sensitive silver iodobromide emulsion (containing 6 moles of silver iodide) as a hardening agent], 2-bis(vinylsulfonyl J ethane 2'j6 bath solution C water: methanol = 1
: 1) In addition to 1201d', samples 11 to 17 were coated and dried on a subbed transparent polyester base.
i created L&. (Coated silver Jt20i+P/ 1.00 C
11) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following phenomenon treatment. The results are shown in Table 1.

[Processing process] (38℃ processing time Color development 3 minutes 15 seconds Bleach 1 minute water Washing 3 minutes 15 seconds Fixing 6 minutes water Washing 3 minutes 15 seconds Stabilizing bath 1 minute processing solution used in the processing process The composition was as follows.

[Color developer composition]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75# Anhydrous sodium sulfite 4.25. P Hydroxyamine 1/2 sulfate 2.0.9 Anhydrous potassium carbonate 37.5.9 Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5II Potassium hydroxide i, oI! Add water to make it 1 NO, and use potassium hydroxide to pH 10.
, adjust to 0.

[Bleach solution composition]

Ethylenediaminetetraacetic acid iron ammonium salt 100.
0. ! i' Ethylenediaminetetraacetic acid diammonium salt 10.0
11 Ammonium bromide 150.0! ! Glacial acetic acid 10. Add □ml water to bring the pH to 11, and use ammonia water to pH'6.
．． Adjust to Q.

[Fixer composition]

Ammonium thiosulfate (50% aqueous solution) 162 ml Anhydrous sodium sulfite 12.4.9 Add water to make 11 and adjust to pt 16.5 using acetic acid.

[Stabilizing liquid composition]

Formal y (37% water solution) 5.01 rLl Konidax (manufactured by Konishiroku Photo Industry Co., Ltd. 1 7.51 nl! Add water to make 11).

Table 1, Box 1 The specific sensitivity is the reciprocal of the exposure amount that exceeds the density of Capri density factor 0.1, and Sample 11 using Comparative Coupler 1 was set as 100.

The sample was placed in a sealed container for 3 days to which 6 cc of 9% formalin hemorrhoid solution, whose temperature and humidity were controlled to 230° C. and 62% RH, was subjected to color development.

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

Comparative coupler 1 Comparative coupler 2 Comparative power puller 4 As shown in Table 1, comparative coupler 1 has a structure similar to the coupler of the present invention, and has a sensitivity, maximum density,
Although good results were shown for both formalin resistance, the results were still insufficient to meet the requirements of the present inventors. Comparative coupler 21-j It has a structure more similar to the coupler of the present invention than Comparative coupler 1, and is a coupler in which the 6th position of the pyrazolotriazole mother nucleus is hydrogen, but it has comparative sensitivity, maximum concentration, and formalin resistance. The level was extremely low.

Comparative coupler 3 is a compound in which the 1st position of comparative coupler 2 is substituted with the active site of a compound having an active methylene group, and is a compound with improved formalin resistance. However, although a slight improvement was observed in both specific sensitivity and maximum density, it was at a low level, and although an improvement was observed in formalin resistance, it was still insufficient. Comparative coupler 4 is a compound in which the 6th position of comparative coupler 3 is substituted with a fluoro atom, and the specific sensitivity,
It is a compound with maximum concentration and improved formalin resistance,
It was still insufficient.

According to the results in Table 1, in order for Comparative Pullers 2, 3, and 4, which have the same group as the diffusion-resistant group of the present invention, to satisfy all of the sensitivity, maximum concentration, and formalin resistance, It is necessary that the 1st position of the pyrazolotriazole mother nucleus is hydrogen, and that the 6th position is substituted with a group capable of coupling with the oxidized product of the coloring agent, such as a chloro atom. be.

Furthermore, although the above-mentioned requirements were satisfied in Comparative Force Puller 1, the results obtained were still unsatisfactory. It is understood from this that the effects of the present invention are completely surprising.

[Example-2] The magenta coupler of the present invention and the comparative coupler were prepared in the same manner as in Example-1, and samples 21 to 27 were prepared.
Processed. The results are shown in Table 2.

Table 2 X3 The specific sensitivity has the same meaning as the specific sensitivity in Table 1, and shows the value when the sensitivity of Sample 21 using Comparative Coupler 5 is set to 100.

Comparative power coupler 5 Comparative coupler 6 As shown in Table 2, comparative coupler 5 is a coupler that has been used practically in the past, but it has low sensitivity and maximum density, and also has poor storage stability, especially formalin resistance. I'm so happy with the result. Although the sensitivity was improved, the scolding coupler 6 had poor maximum concentration and formalin resistance. Comparative coupler 7 showed improvement in maximum density and formalin resistance, but was still insufficient in sensitivity.

From these results, it can be seen that nothing has yet been found that satisfies all of the sensitivity, maximum concentration, and formalin resistance. However, in the coupler of the present invention, the formalin resistance showed a value almost equivalent to Comparative Coupler 7, and the specific sensitivity and maximum density showed high values in both cases. It is understood that the effects of the present invention are completely unexpected and serious.

■ Effects of the Invention As shown in Examples 1 and 2, the magenta coupler of the present invention has high sensitivity and high color density, and is also stable during storage, especially in the presence of formalin. Since it is a filler that exhibits color-forming properties, it is necessary to add phenol or By adding naphthol-based cyan couplers to red-sensitive silver halide fL agents and coating them on a transparent support using various additives as appropriate, a completely new type of silver halide color photographic photosensitive material with stable color balance is produced. I was able to borrow materials.

Agent Yoshimi Kuwahara

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least a magenta coupler represented by the following general formula CI) is contained in the silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized by containing one of the following: General formula [I] (Y)n [wherein R1 represents an alkyl group or an aryl group,
R2 represents a monovalent group, R3u represents an alkylene group, Y represents a halogen atom, hydroxy group or alkyl group, and z represents a group that can be eliminated by a coupling reaction with an oxidized form of the color-forming agent. , l represents an integer from 1 to 5, m represents an integer from 0 to 4, and n represents an integer from 0 to 5.
each represents an integer. ]