JPH03125143A - Silver halide color photographic sensitive material containing magenta coupler - Google Patents

Abstract

PURPOSE:To provide excellent color developability, amendment of deviation in color tones by densities and improved color reproducibility by incorporating a specific magenta coupler into at least one layer of silver halide emulsion layers. CONSTITUTION:This photosensitive material contains the magenta coupler expressed by formula I in at least one layer of the silver halide emulsion layers. In the formula, R1 to R5 denote a substituent; at least one of R2, R3, R4 is expressed by formula II and a group having at least one of -COOM (M is a hydrogen atom, cationic radical) groups; l denotes 0 to 2; R5 may be the same or different when l is 2; X denotes an elimination group. Y denotes an oxygen atom or sulfur atom; m, n, p, q respectively denote 0 or 1; R6 denotes an alkyl group or aryl group; R7 denotes a hydrogen atom or alkyl group, etc. The fluctuation in the color tones by the densities is lessened in this way and the sufficient color developing density is obtd. even with a color developing soln. of low pH. The excellent color developability and the good color reproducibility are obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material containing a magenta coupler, and more specifically, the present invention relates to a silver halide photographic light-sensitive material containing a magenta coupler. The present invention also relates to a silver halide photographic material from which dye images with excellent color development can be obtained.

[Background of the Invention] Couplers commonly used in silver halide color photographic materials include yellow couplers made of open-chain ketomethylene compounds, magenta couplers made of pyrazolone compounds and pyrazoloazole compounds, phenol compounds, and naphthol compounds. A cyan coupler consisting of the following is known.

Conventionally, pyrazolone compounds have been frequently used as magenta couplers, but dyes formed from pyrazolone magenta couplers have undesirable side absorption, and improvement thereof is desired.

In addition, in order to solve this problem, U.S. Patent No. 3゜725.0
No. 65, No. 3,810,761, No. 3.758,30
Pyrazolotriazole couplers are proposed in the specifications of No. 9 and No. 3,725,067. However, this pyrazolotriazole coupler with low side absorption is not sufficient in terms of color development, and research continues with the aim of improving color development.
It is described in various publications such as No. 0-98434 and No. 61-120152. However, it has become clear that most of the pyrazolotriazole couplers described in the above-mentioned prior art exhibit different color tones depending on the color density when used in silver halide photographic materials. More specifically, it has been revealed that as the color density increases, the density on the short wavelength side increases (the short wavelength side protrudes) from the maximum absorption density, causing a decrease in color reproducibility.

Among the pyrazolotriazole couplers that have been studied so far, there are also pyrazolotriazole couplers that do not cause the above problem (color tone shift due to density).
This is a coupler described in publications such as No. However, even with the above-mentioned pyrazolotriazole couplers that have improved the problem of color tone deviation due to concentration, they are still insufficient in terms of color development. The development of zolotriazole couplers is desired.

[Objects of the Invention] The first object of the present invention is to provide a silver halide color photosensitive material that is a pyrazolotriazole coupler and has excellent color development, improved color tone deviation due to density, and good color reproducibility. There is a particular thing.

A second object of the present invention is to provide a pyrazolotriazole coupler that exhibits less variation in color development with respect to pH variations in a processing solution.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the general formula [ This was achieved by a silver halide photographic material characterized by having a magenta coupler represented by I].

General formula [11 [wherein R, to R5 represent a substituent, R,, R3
, at least one of R4 is represented by the general formula [II] and represents a group having at least one -C00M (M is a hydrogen atom, a cationic radical) group;
In, 1 represents 0 to 2, and when 1 is 2, R
s may be the same or different, and X represents a leaving group.

General formula [I summer] -(J+)--(J2). -(Js) p-(J4)
q-Ra [wherein J, ~J4 are alkylene, aryle]
NCO--COO--0CO- R7SO2--NHCNH--NHCOO- (Y is an oxygen atom or a sulfur atom), and ms ns P and q each represent 0 or 1. Further, R6 represents an alkyl group or an aryl group,
R2 represents a hydrogen atom, an alkyl group, or an aryl group. [Specific Structure of the Invention] The pyrazolotriazole coupler represented by the general formula [I] used in the present invention will be explained in more detail.

In general formula [I], R3 represents a substituent, such as a primary alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, decyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc.), secondary or tertiary alkyl group (isopropyl group,
5ec-butyl group, 2-methyl-butyl group, 2-hexyl-nonyl group, t-butyl group, t-pentyl group, 2゜2
These primary, secondary, and tertiary alkyl groups may further have substituents, such as halogen atoms (fluorine atoms, chlorine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, n-pentyl group, t-amyl group, n-hexyl group, n
-hebutyl group, n-octyl group, n-decyl group, etc.), alkenyl group (vinyl group, etc.), alkynyl group (1-propynyl group, etc.), aryl group (phenyl group, 4-t-butylphenyl group, 2, 4-di-t-amylphenyl group, etc.), heterocyclic group (2-furyl group, 2-thienyl group, etc.), cyano group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, 2-methanesulfonylethoxy group, n-butoxy group, etc.), aryloxy group (phenoxy group, 2.4-
di-t-acylphenoxy group, etc.), acyloxy group (acetoxy group, hexadecanoyloxy group, etc.), acylamino group (acetamide group, benzamide group, α-(2,
4-di-t-acylphenoxy)butyramide group, etc.),
Anilino group (phenylamino group, etc.), amino group (ethylamino group, dimethylamino group, etc.), sulfonyl group (methanesulfonyl group, hexadecanesulfonyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), alkoxycarbonyl group ( methoxycarbonyl group, ethoxycarbonyl group, etc.).

Other examples of R2 include aryl groups (phenyl groups, etc.),
Alkylthio group (methylthio group, octylthio group, etc.),
Arylthio group (phenylthio group, etc.), anilino group (phenylamino group, etc.), acylamino group (acetamido group, benzamide group, etc.), alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), ureido group (methylureido group,
phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), and these substituents may further have a substituent, and the substitution Examples of the group include the same substituents (described above) when R3 is an alkyl group.

The substituent represented by R1 is preferably an alkyl group, more preferably a primary alkyl group,
Most preferred is a methyl group. Next, the general formula [I]
To explain R8 to R2 in the general formula [1F, R7
-R6 represents a substituent, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a carbon atom number of 1 to
22 straight chain, branched or cyclic alkyl groups (e.g. methyl, ethyl, isopropyl, t-butyl, octadecyl, cyclohexyl), aryl groups (e.g. phenyl, naphthyl), alkoxy groups (e.g. methoxy) , ethoxy group, dodecyloxy group), aryloxy group (e.g. phenoxy group, naphthoxy group), acyloxy group (e.g. acetoxy group, benzoyloxy group),
Alkylthio groups (e.g. methylthio group, dodecylthio group), arylthio group (e.g. phenylthio group), amino group (e.g. methylamino group, diethylamino group, anilino group), cyano group, nitro group, hydroxyl group, carboxyl group, acylamino group (e.g. acetamino group). , benzamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group), ureido group (
For example, methylureido group, phenylurei-γ group), carbamoyl group (for example, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group), sulfur
moyl group (e.g. dimethylsulfamoyl group, dodecylsulfamoyl group, phenylsulfamoyl group), acyl group (e.g. acetyl group, benzoyl group), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, octadecyloxycarbonyl group), heterocyclic group (
Examples include 2-furyl group, 2-thionyl group, 2-pyrimidinyl group, etc.).

These groups may further have a substituent, and examples of the substituent include the aforementioned halogen atom, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acylamino group, sulfonamide group,
Examples include ureido group, carbamoyl group, sulfamoyl group, and sulfonyl group.

As the substituents represented by R2 to R8, preferable substituents are an alkyl group, a halogen atom, an acylamino group, and a sulfonamide group, more preferably an alkyl group, and an especially preferable one is a methyl group. General formula [I]
In, at least one of R7 to R5 is represented by the general formula [I! ] and at least one 1000M
(M represents a hydrogen atom or a cationic radical), and R4 is preferably monovalent.

Next, general formula [II] will be explained.

General formula [I! ] −(Jl), −(, tz)n−(JsL−(J4), t
-Ra general formula [■! ], J1 to J4 are each an alkylene group (e.g. methylene group, ethylene group, trimethylene group, etc.), an arylene group (phenylene group, etc.), (of the substituents, R2 is a hydrogen atom, an alkyl group, an aryl group) (Y is an elementary atom or a sulfur atom.)
represents a divalent group, and the above alkylene group, arylene group%
R? may further have a substituent, and examples of the substituent include the same substituents as in the case where R in the above-mentioned general formula [I] is an alkyl group.

Also, general formula [! ! ], R6 is an alkyl group (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group) , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopentyl group, cyclohexyl group, etc.)
, represents an aryl group (phenyl group, etc.). At this time, the alkyl and aryl groups may further have a substituent, and the substituent includes R1 in the general formula [1] above.
The same substituents as when is alkyl are mentioned. Furthermore, the monovalent group represented by the general formula [II] has at least one -COOM (M is a hydrogen atom, a cationic group)
However, the -C00M group is J in the general formula [II].

It may be introduced by directly substituting J2, Js, Ja, Ja, or it may be introduced via a divalent group in J, %J2, J, , J4, J.

A particularly preferred monovalent group represented by the general formula [II] is a monovalent group (having at least one -COOM group) represented by the Fukishita general formula [III].

General formula [III] -(Js)-(Ja)F-Re [wherein J,
represents -NHCO-, -NHSO2-, Ja
is alkylene, arylene, -N)ICO-, -NHS
It represents O2-, and R6 has the same meaning as R6 in the general formula [TI]. r is O~2, and when r=2, Ja may be the same or different. ] Next, X in general formula [1] will be explained.

X is a group that can be separated by a coupling reaction with an oxidized color developing agent, such as a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, an oxygen atom, a nitrogen atom, and a sulfur atom. Represents a group of atoms required to form a 5- or 6-membered ring with an atom selected from among atoms. ) etc.

Specific examples are given below.

Halogen atoms: atoms such as chlorine, bromine, and fluorine Alkoxy groups: ethoxy group, benzyloxy group, ethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrosoenoxy group Acyloxy groups: acetoxy, myristoyloxy, benzoyloxy, etc. Arylthio groups: phenylthio, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group, ethoxyethylthio group, phenoxy group Examples include tilthio groups and the like.

As X, a halogen atom is particularly preferable, and a chlorine atom is particularly preferable.

Typical specific examples of magenta couplers according to the present invention are shown below, but the present invention is not limited thereto.

Margin below 1 C1moss 0 1 2 3 14 5 9 0 1 ShiZ 6 7 8 2 3 4 C1toss meeting C1&ll33 CI@lI35 5 26 7 1 2 3 LSI・1111 8 9 0 4 5 6 37 3 days 9 Typical synthesis examples of the compounds of the present invention are shown below.

<Synthesis example> Exemplary compound (1) synthesis of N-N tl Shil+3 Edge: 0 1 ― CIJ3? Shinko +111° (1) 1 c+5nss Next, an example of synthesis of the compound used in the present invention will be shown.

[Synthesis Example] Compound (Organic 5ynthes) shown in Synthesis 1 of Exemplified Compound (1)
isV.

It was synthesized by the method described in 15.706. ) 5og was dissolved in concentrated sulfuric acid 200 ■1, cooled with water, and 61%
) A mixed solution of 31.5 g of lHOs and 200 mfL of concentrated sulfuric acid was added dropwise over 3.5 hours. After the dropwise addition, the mixture was stirred for 30 minutes.
The mixture was poured into 1 fL of ice. The precipitated solid was filtered, washed with water, and then dried. Add this to 200mj of ethanol! and water 1
Recrystallization from a mixed solvent of 00 mf gave 38.4 g of the compound represented by 2.

To 32.7 g of the compound represented by 2 was added 22.7 g of thionyl chloride.
7.1 was added and the mixture was heated and refluxed for 2 hours, and then concentrated under reduced pressure.

140 ta of ethyl acetate was added to 27.4 g of the compound represented by 3.
A solution of fl and 21.9 g of potassium acetate in 88IIIL of water was added, and the above acid chloride was added dropwise. After stirring for 2 hours, the precipitated solid was filtered, washed with water, then with ethyl acetate, and then dried. Compound 45.3 represented by 4
I got g.

Add 300IIIL of ethyl acetate to 40g of the compound shown by the hill.
and 25.4 g of thionyl chloride were added, and the mixture was heated under reflux for 1.5 hours. Extraction was performed by adding water and ethyl acetate. After washing the ethyl acetate layer three times with water, 21.3 g of potassium hydrogen carbonate and 8
5 and 1 solution was added, and the mixture was heated under reflux for 1 hour. The ethyl acetate layer was taken, washed with water, and then concentrated under reduced pressure. The residual solid was washed with acetonitrile to obtain 35.4 g of the compound shown below.
I got it.

33g of the compound represented by 5 and 16.5+*J2. Concentrated sulfuric acid L6. Add S ml and vinegar @55+ajL, 14
Heat to reflux for an hour. The solid was poured into ice water 60081, and the precipitated solid was filtered, washed with water, and then recrystallized from 800 L of methanol to obtain 23.9 g of the compound represented by 6.

11.7 g of the compound represented by 6 was dissolved in 230 μl of dimethylformamide, and 60 mft of water and 60 μL of aqueous ammonia were added and heated. 35.1 g of sodium hydrosulfide was added to this and stirred for 30 minutes. After neutralizing with hydrochloric acid, it was concentrated under reduced pressure.

Recrystallize the residue from methanol to obtain compound 6
．． 1g was obtained.

5.5g of the compound shown in F was added to 50sj of chloroform!
Dissolve in 20 ml of N,N-dimethylformamide,
- 2.9 g of chlorosuccinimide was added in portions. After that, chloroform was distilled off, ethyl acetate was added and washed with water, and the ethyl acetate layer was dried with magnesium sulfate.
The solvent was distilled off to obtain 5.6 g of the compound represented by 8.

3.2 g of the compound represented by 8 in 35 mj2 of toluene,
0% pyridine, 3.8 g of octadecenylsuccinic anhydride was added, and the mixture was heated under reflux for 3 hours. After cooling, the solid obtained by filtration was dissolved in acetonitrile/alcohol.
171 to obtain 1.8 g of compound (1).

The coupler used in the present invention is usually 1 mole to 1X10-' mole per 1 mole of silver halide, preferably 1X10-' mole.
It can be used in the range of -2 mol to axio-' mol.

The coupler of the present invention can also 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 composition 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 a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane 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 3
A vine with a diameter of 0μ, preferably 0.1 to 20μ is used.

The silver halide emulsion may have any grain size distribution, and may be an emulsion with a wide grain size distribution (referred to as a polydisperse emulsion), or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). ) may be used alone or in combination.

Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The couplers used in the present invention include a colored coupler having a color correction effect and a development inhibitor, a development accelerator, a bleach accelerator, a developer, and a silver halide solvent by coupling with an oxidized form of a developing agent. Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers are included.

Among these, a so-called DIR compound may be used, which releases a development inhibitor during development and improves image clarity and image graininess.

These DIR compounds include those in which the inhibitor is directly bound to the coupling position, and those in which the inhibitor is bound to the coupling position via a divalent group, and the intramolecular nucleophile in the makuuchi separated by the coupling reaction. Bonded in such a way that the inhibitor is released by reaction or intramolecular electron transfer reaction (timing DI
It is called R compound. ) is included. In addition, there are two types of inhibitors: those that are diffusible after withdrawal and those that are not so diffusive.
They can be used alone or in combination depending on the purpose.

A colorless coupler (also referred to as a competitive coupler) which undergoes a coupling reaction with an oxidized product of an 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 tacetanilide couplers are preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used.

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

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsions of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant may also be used to prevent graininess from becoming 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 DR17843.

Wood-philic colloid layers such as protective layers and intermediate layers of photosensitive materials contain an ultraviolet inhibitor to prevent fogging 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 too.

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 paper, color reversal films, and the like.

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

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing.

Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleaching solution and the process using a fixing solution. In addition, a bleach-fixing process can be carried out using a -bath bleach-fixing solution, or a monobath process can be carried out using a monobath developing, bleaching-fixing solution for color development, bleaching and fixing.

[Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to this embodiment.

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. Ethyl acetate was added and heated to 60°C to completely dissolve.

This solution was mixed with 1200 tJ of a 5% aqueous gelatin solution containing 120 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Depont). Then, this dispersion was added to 4 g of a green-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide) and used as a hardening agent. 1.2% solution of 2-bis(vinylsulfonyl)ethane (water:methanol=1:1) 120mj
! Samples 1 to 12 were prepared by coating and drying on a subbed transparent polyester base.

(Amount of coated silver: 20 mg/locm'') 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°C 3 minutes 15 seconds Bleaching 38°C 4 minutes 20 seconds Washing 38°C 3 minutes 15 seconds Fixation 38°C 4 minutes 20 seconds Water washing 38°C 3 minutes 15 seconds Stabilization
Drying at 38°C for 1 minute and 30 seconds. Drying at 47°C ± 5°C for 16 minutes and 30 seconds. The composition of the treatment liquid used in each treatment step is as follows.

(Color developer composition) Potassium carbonate 30.0g Sodium bicarbonate 2.5g Potassium sulfite 5.0g Potassium bromide 1.3g Potassium iodide
2.0g Hydroxylamine sulfate 2.5g Sodium chloride
0.6g Sodium diethylenetriaminepentaacetate 2.583-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to bring the total amount to tU and adjust the pH to 0.06 using potassium hydroxide or 20% sulfuric acid.

(Bleach solution composition) Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid iron 10.0g Ammonium bromide 150.0g Glacial acetic acid
40.0m! Sodium bromide 10.0g IJ by adding water:
Adjust the pH to 3.5 using L and C, aqueous ammonia or glacial acetic acid.

(Fixer composition) Ammonium thiosulfate 180.0 g Anhydrous sodium sulfite 12.0 g Sodium metabisulfite Disodium ethylenediaminetetraacetic acid Sodium carbonate water was added to make 14.

(Stabilizing liquid composition) Formalin (37% aqueous solution) Konidax (Konica 14) Add water to make 11.

2.5 g 0.5 g 10.0 g 2.0 g 5.0 g Table 1 1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and the sample using comparative coupler 1 was set as 100.

2) λ at concentration, 1. The absorbance at a wavelength shorter than 25nI11 is As? When the absorbance of s λ,,8 is A g,,l, Comparative coupler 1 Comparative coupler 2 Comparative coupler 3 Comparative coupler 4 12H2S As is clear from Table 1, the sample according to the present invention has no decrease in sensitivity. It was confirmed that the maximum density was high and there was little deviation in color tone due to density.

Example 2 A multilayer color photosensitive material was prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide.

Incidentally, the amount added in the photosensitive material is shown per 100 cm'.

(1) 20 mg of gelatin, 5 mg of silver as a blue-sensitive silver chlorobromide emulsion (containing aO mol% silver bromide), and 8 m
g of yellow coupler* and 0.1 mg of 2°5-di-t-octylhydroquinone, 3 mg of dioctyl phthalate.

(2) 12 mg gelatin, 0.5 tsg of 2.5-
Di-t-octylhydroquinone and 4 mg of UV absorber*, 2 mg of dibutyl phthalate in paleolayers.

(3) 18 mg of gelatin, 4 mg of silver as a green-sensitive silver chlorobromide emulsion (containing 70 mol% silver bromide), and 5 m
g of magenta coupler* and 2IIg of antioxidant* and 0.2 B of 2.5-di-t-octylhydroquinone and 2.5 B of dioctyl phthalate.

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

(s) gelatin of ia heat g, red-sensitive silver chlorobromide emulsion (containing 70 mole % silver bromide) with silver content of 4B, and 3.5
mg of cyan coupler* and 0.1 mg of 2.5
- Di-t-octylhydroquinone, 2.0B1g of tricresyl phosphate in paleolayer.

(6) Protective layer containing 9s+H gelatin.

*As the ultraviolet absorbers (2) and (4), UV-1 and UV-2 having the structures described below were mixed (mixing ratio 1:1) and used.

*As the antioxidant (3), di-t-pentylhydroquinone di-octyl ether was used.

After the above-mentioned multilayer photosensitive material was subjected to wedge exposure according to a conventional method, the following development treatment was performed.

Table 2 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.

(Development process) Color development 38℃ 3 minutes 30 seconds bleach fixing
Stabilization treatment at 38°C for 1 minute and 30 seconds/or washing treatment at 25°C to 30°C for 3 minutes Drying at 75°C to 80°C for 2 minutes The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol 15mj Ethylene glycol 15mj Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride
0.2g potassium carbonate
30.0g hydroxylamine sulfate 3.0g polyphosphoric acid (TPPS)
2. sg3-methyl-4-amino-N-
Ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 5.5g 1.0g Potassium hydroxide 2.0g Add water to IL and adjust p) I to 11.08.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% solution) 100 mil ammonium sulfite (40% solution) 27.5++1' glacial acetic acid
Adjust the pH to 7.1 with 10.0 mN 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-hydroxyethylidene-1,1- 1.0 g Disulfonic acid Add 2.0 g of water and bring to 1°C, and add sulfuric acid or potassium hydroxide. pH7.0 at
Adjust to.

1) The specific sensitivity is the reciprocal of the exposure amount that gives a density with a fog density factor of 0.11, and is set to 100 for sample 201 using a comparative coupler.

2) The sample after the color development process was exposed to a xenon fade meter for 5 days to show the percentage of dye remaining after the process at the initial density D=1.0.

3) The definition of tone variability is the same as in Example 1.

-1 -2 -2 -3 -1 From the results shown in Margin Table 2 below, it was confirmed that the sample according to the present invention had no decrease in sensitivity, had a high maximum density, and had a small deviation in color tone due to density. .

Furthermore, the dye image obtained according to the present invention was found to have excellent light fastness.

Example 3 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially coated from the support side to prepare sample 301 of a multilayer color photographic material.

Incidentally, the amount added in the silver halide photographic light-sensitive material is the amount per 112 unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

1st layer; antihalation layer (HC) Gelatin layer containing black colloidal silver.

Second layer; Intermediate layer (IL) 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 0.30μ■, containing 8g AgI 6.0mol%
Monodispersed emulsion (emulsion... silver coating amount: 1.
8g/m2 sensitizing dye■... 6 x 10'' sensitizing dye per 1 silver!!・
... 1 mole of silver. OX 10-'Morsian Cutler (C-2)... 0.06 mol per mol of silver Colored cyan coupler (CC-t)... 0.003 mol DIR compound per mol of silver ( D-1)... 0.0015 mol per mol of silver DIR compound (D-2) -... 0.002 mol per mol of silver 4th layer; Highly sensitive red-sensitive silver halide emulsion layer (RH) Average particle size 0.5μ■, 8gBr containing 7.0mol%
Monodisperse emulsion consisting of 1 (emulsion II)...silver coating amount 1
．． 3 g/m" Sensitizing Dye 1... 3 x 10-' mol Sensitizing Dye II per 1 mole of silver
... For 1 mole of silver 1. OX 10-5 mol cyan coupler (C-5)... 0.02 mol per mol of silver Colored cyan coupler (CG-1)... 0.0015 mol DIR compound (D -2)... 0.001 mol per mol of silver Fifth layer; Intermediate layer (!L) A gelatin layer with the same composition as the second layer.

6th layer: Low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I... coated silver amount 1.5 g/a2 Sensitizing dye III... 2.5X 10-' mole increase per mole of silver Sensitive pigment ■・
... 1.2X 10-' mole magenta coupler (M-1) for 1 mole of silver... 0.050 mole for 1 mole of silver Colored magenta coupler (CM-1)... for 1 mole of silver 0.009 mol DIR compound (D-1)... 0.0010 mol relative to 1 mol of silver DIR compound (D-3)... 0.0030 mol relative to 1 mol silver 7th layer; High-sensitivity green-sensitive silver halide emulsion layer (GH) Emulsion II... coated silver amount 1.4 g/a2 sensitizing dye I11...
- 1.5X 10-' mole sensitizing dye i per mole of silver
v... per mole of silver 1. OX 10-' mol Magenta coupler (M-1)... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.002 mol DIR compound (D -3)... 0.0010 mol per mol of silver 8th layer: yellow filter layer 9th layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-7-octylhydroquinone; gelatin layer.

Low-speed blue-sensitive silver halide emulsion layer (BL) average grain size 0.
Monodispersed emulsion (emulsion m) consisting of AgBr1 containing 48 μm% AgI and 6 mol%...silver coating amount 0.9 g/m2 10th layer sensitizing dye ■... 1.3X per mole of silver 10- 'Mole yellow coupler (Y-3) ... 0.29 mol per 1 mol of silver; high sensitivity blue-sensitive emulsion layer (BH) average grain size 0.8 μm 1^gI 8 gB containing 15 mol%
Monodisperse emulsion consisting of rl (emulsion ■)...silver coating amount 0.
5g/m2 Sensitizing dye V... 1.0 g/m2 per mole of silver. OX 10-' mol Yellow coupler (Y-3)... 0.08 mol per mol of silver DIR compound (D-2)... 0.0015 mol per mol of silver 11th layer; 1 protective layer (Pro-1) Silver iodobromide (AgI 1 mol%, average grain size 0.7 μm)
・・Silver coating amount 0.5g/m” UV absorber tlV-1,
Gelatin layer containing UV-2 (1:1).

12th layer; second protective layer (Pro-2) polymethyl methacrylate particles (average particle size 1.5 μm)
and a gelatin layer containing formalin scavenger (++5-1).

In addition to the above ingredients, each layer contains a gelatin hardening agent ().
I-1) and a surfactant were added.

Furthermore, M-1 contained in layer 6 and layer 7 in sample 301
Sample 301 except that the coupler was changed to the coupler shown in Table 2.
Samples 302 to 307 were prepared in the same manner.

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

Sensitizing dye ■: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide; Anhydro-9-ethyl-3,3'-di(3- sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide; anhydro5,5'-diphenyl-9-ethyl-3
,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■;Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,'6.5',6'- Dibenzoxacarbocyanine hydroxide; unstretched draw 3.3'-di(3-sulfopropyl)
-4,5-benzo-5'-methoxythiacyanine hydroxide sensitizing dye V Sensitizing dye ■ Sensitizing dye 111 Below margin M-1 -3 S-1 -1 1(-1 [Bleach solution [Fixer ] The following margins Samples 11 to 18 thus obtained were subjected to wedge exposure using white light, and then the following development treatment [II] was performed.

Processing step [1] (38℃) IA waiting time Color development 3 minutes 15 seconds Bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilization 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 developer] to arrange.

[Stabilizer] Separately developed [Developed in the same manner as II except that the pH of the color developing solution in II was adjusted to 9.76]
II] was carried out.

These results are shown in Table 3.

1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1, and sample 301 using M-1 was set as 100.

2) Values for specific sensitivity, maximum density, and color tone variability are measured values in development process [I].

3) Processing variability was determined using the following formula.

4) The definition of tone variability is the same as in Example 1.

As is clear from the results in Table 3, the couplers used in the present invention have superior color development properties, less variation in color tone due to concentration, and sufficient color development density even with low pH color developing solutions compared to comparative couplers. I found out that I can get it.

[Effects of the Invention] The silver halide photographic material containing the magenta coupler used in the present invention has little variation in tone due to density, and
And sufficient color density can be obtained even with a low po color developer,
Excellent color development and good color reproducibility. Furthermore, it has excellent light resistance.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a magenta compound represented by the general formula [I]. A silver halide photographic material characterized by having a coupler. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 to R_5 represent substituents, R_2
, R_3, and R_4 represent a group represented by the general formula [II] and having at least one -COOM (M is a hydrogen atom, a cationic radical) group. In the general formula [I], l represents 0 to 2, and when l is 2, R_5 may be the same or different, and X represents a leaving group. General formula [II] -(J_1)_m-(J_2)_n-(J_3)_p-
(J_4)_q-R_6 [In the formula, J_1 to J_4 are alkylene, arylene, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COO-, -O
CO-, -SO_2-, ▲Mathematical formulas, chemical formulas, tables, etc.▼,-
NHCOO- (Y is an oxygen atom or a sulfur atom), and m, n, p, and q each represent 0 or 1. Further, R_6 represents an alkyl group or an aryl group, and R_6 represents an alkyl group or an aryl group, and R
_7 represents a hydrogen atom, an alkyl group, or an aryl group. ]