JPH10161285A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an silver halide color photographic sensitive material excellent in color forming property and ensuring improved light fastness of a magenta dye image by incorporating a specified magenta coupler into a green-sensitive silver halide emulsion layer. SOLUTION: This silver halide color photographic sensitive material has photographic constituent layers including blue-, green- and red-sensitive silver halide emulsion layers on the substrate and at least one kind of magenta coupler represented by the formula is contained in at least one of the green-sensitive silver halide emulsion layers. In the formula, R1 is a substituent, R2 is H, alkyl or aryl, R3 is alkyl, aryl, -CO2 R4 , -CONHR4 , -NHCOR4 , -NHCONHR4 , -NHR4 , -N(R4 )2 , -SR4 , -SO2 R4 or -NHSO2 R4 , R4 is alkyl or aryl, each of the alkyl and aryl may have a substituent and X is H or a group releasable by reaction with the oxidized body of a color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler. More specifically, the invention contains a novel pyrazolotriazole-based magenta coupler to provide excellent color reproducibility and coloring. And a silver halide color photographic light-sensitive material capable of obtaining a dye image stable to heat and light.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, couplers generally used include a yellow coupler composed of an open-chain ketomethylene compound, a magenta coupler composed of a pyrazolone compound and a pyrazoloazole compound, a phenol compound and a naphthol compound. Cyan couplers composed of compounds are known.

Heretofore, 5-pyrazolone compounds have been frequently used as magenta couplers. Known pyrazolone magenta couplers include U.S. Pat.
Nos. 88 and 3,519,429, JP-A-49-111
No. 631, No. 57-35858 and the like.
However, the Theory of the Photographic Process (The Theory of the P
Photographic Process), Macmillan, 4th edition (1977), pp. 356-358, Fine Chemicals, CMC, vol. 14, No. 8, 38.
As described in the Abstracts of the Photographic Society of Japan, Annual Meeting of 1985, pp. 108-110, dyes formed from pyrazolone magenta couplers have undesirable side absorption, and improvement thereof is desired. ing.

As described in the above literature, a dye formed from a pyrazoloazole magenta coupler has no side absorption. The fact that this coupler is a good coupler has been shown in the prior literature as U.S. Pat. No. 3,725,067,
Nos. 3,758,309 and 3,810,761 are also described.

However, the light fastness of azomethine dyes formed from these couplers is remarkably low, which significantly impairs the performance of color photographic light-sensitive materials, especially print-based color photographic light-sensitive materials.

[0006] Conventionally, studies have been made to improve the light fastness. For example, JP-A-59-12573
No. 2, 61-282845, 61-29239
And JP-A-61-279855 disclose a technique of using a phenolic compound or a phenyl ether compound in combination with a pyrazoloazole-based magenta coupler.
No. 6, No. 62-208048, No. 62-157031
And No. 63-163351 disclose a technique using an amine compound in combination.

Further, JP-A-63-24256 proposes a pyrazoloazole-based magenta coupler having an alkyloxyphenyloxy group.

However, even in the above technique, the light fastness of the magenta dye image is insufficient, and improvement thereof has been strongly desired.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a halogen which is excellent in color development and has a markedly improved light fastness of a magenta dye image. An object of the present invention is to provide a silver halide color photographic material.

[0010]

The above objects of the present invention have been attained by the following constitutions.

1. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support; A silver halide color photographic material comprising at least one emulsion layer containing at least one magenta coupler represented by the following formula (I).

[0012]

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[Wherein, R ₁ represents a substituent, R ₂ represents a hydrogen atom, an alkyl group or an aryl group, and R ₃ represents an alkyl group, an aryl group, —CO ₂ R ₄ , —CONHR ₄ , and —N
_{HCOR 4, -NHCONHR 4, -NHR 4} , -N
_{(R 4) 2, -SR 4} , -SO 2 R 4 or -NHSO ₂ R ₄
And R ₄ represents an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. Hereinafter, the present invention will be described specifically.

The substituent represented by R _{1 in the} general formula (I) includes alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, Carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino, alkylamino, anilino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, Each group such as carboxyl, a halogen atom and the like are preferable, and an alkyl group is more preferable, and a t-butyl group is particularly preferable.

The alkyl group represented by R ₂ , R ₃ and R ₄ preferably has 1 to 32 carbon atoms, and may be straight-chain or branched.

The aryl group represented by R ₂ , R ₃ and R ₄ is preferably a phenyl group.

The alkyl group or the aryl group represented by R ₂ , R ₃ and R ₄ can have a substituent represented by R ₁ .

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy,
Aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio,
Arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,
And the like, but a halogen atom is preferable, and a chlorine atom is particularly preferable.

Hereinafter, typical specific examples of the magenta coupler represented by formula (I) of the present invention will be shown, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025] The pyrazoloazole-based magenta coupler of the present invention can be obtained from the Journal of the Chemical Society (Journal of the Chemical Society).
alSociety), Perkin I
(1977), 2047-2052, U.S. Pat.
5,067, JP-A-59-99437, and JP-A-58-4
No. 2045, No. 59-162548, No. 59-171
No. 956, No. 60-33552, No. 60-43659
No., 60-172982, 60-190779
Nos. 61-189538 and 61-241754
Nos. 63-163351 and 62-157031
No., Synthesis, 1981, p. 40, 198
4 years 122 pages, 1984 894 pages, JP-A-49-5
No. 3574, British Patent 1,410,846, New Laboratory Chemistry Course 14-III, pp. 1585-1594 (197)
7), Maruzen, Helv. Chem. Acta. , 36
Volume, 75 (1953); Am. Chem. So
c. 72, 2762 (1950); Org. Sy
nth. , Vol. II, p. 395 (1943), and can be easily synthesized by those skilled in the art.

The following is a typical synthesis example of the magenta coupler represented by the general formula (I) of the present invention.

Synthesis Example << Synthesis of Exemplified Compound (I-1) >> Synthesis Scheme

[0028]

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Compound (1) (27.8 g) was dissolved in toluene (150).
and thionyl chloride (17.9 g) was added thereto.
The mixture was heated under reflux for 3 hours. After completion of the reaction, the solvent and excess thionyl chloride were distilled off under reduced pressure to obtain 26.5 g of an intermediate (2). Next, 16.8 g of the compound (3) was added to acetonitrile 20
The mixture was dissolved in 0 ml, and 25.0 g of the compound (2) was added thereto, followed by refluxing for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure.

To the residue, 150 ml of toluene and 2 ml of sulfuric acid
Was added thereto, and refluxed for 2 hours while removing water generated in the ester tube. After completion of the reaction, the solvent was distilled off under reduced pressure.
300 ml of ethyl acetate and 100 ml of a saturated aqueous solution of sodium hydrogen carbonate were added to the residue, and the ethyl acetate layer was separated and extracted. Further, the ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. Thereafter, the ethyl acetate layer was subjected to a reduced pressure treatment to obtain an intermediate (4).

The crude product of the intermediate (4) was added with acetic anhydride 200
Then, the mixture was heated under reflux for 2 hours. Thereafter, heating was further continued while excess acetic anhydride was distilled off, and after the distillation was completed, the reaction solution was cooled to room temperature. 100 ml of methanol and 25 ml of concentrated hydrochloric acid were added thereto, and the mixture was refluxed again for 2 hours. The reaction solution was cooled to room temperature, and the precipitated sulfur was filtered off. The filtrate was concentrated under reduced pressure, 200 ml of ethyl acetate was added, the mixture was neutralized with sodium hydroxide, and the organic layer was extracted. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain a brown oily intermediate (5).
I got

The intermediate (5) was dissolved in 150 ml of a 10% aqueous potassium hydroxide solution and heated under reflux for 3 hours. Thereafter, the reaction solution was concentrated and extracted with ethyl acetate. Thereafter, the ethyl acetate layer was subjected to a reduced pressure treatment to obtain an intermediate (6).

Intermediate (6) was dissolved in 150 ml of ethyl acetate and cooled to 5 ° C. While maintaining the temperature of the reaction solution at 5 to 10 ° C., 6 g of N-chlorosuccinimide was added little by little. After stirring at 5 ° C. for 2 hours, the mixture was washed with water. After separating and extracting the organic layer, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane) to give oily exemplary compound (I-1) 1
2.3 g were obtained.

The identification was carried out by MASS and NMR spectra, and it was confirmed that it was the exemplified compound (I-1).

The magenta coupler represented by the general formula (I) of the present invention can be prepared by the following general formula [A] and / or general formula [B]
Can be used in combination with the image stabilizer represented by

[0036]

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In the general formula [A], R ₅₁ is a hydrogen atom,
Represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and among these, as the alkyl group, for example, methyl,
Examples thereof include linear or branched alkyl groups such as ethyl, propyl, octyl, t-octyl, benzyl, and hexadecyl groups. The alkenyl group represented by R ₅₁ includes, for example, allyl, hexenyl, octenyl and the like. _Examples of the aryl group for R ₅₁ include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R ₅₁ include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups represented by R ₅₁ includes those having a substituent.

R ₅₂ , R ₅₃ , R ₅₅ and R ₅₆ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group, of which alkyl, alkenyl and Groups and aryl groups are the alkyl groups described for R ₅₁ above,
The same as the alkenyl group and the aryl group can be mentioned.
Examples of the halogen atom include fluorine, chlorine, and bromine. Further, as the alkoxy group,
Specific examples include methoxy, ethoxy, and benzyloxy groups. An acylamino group is represented by R ₅₇ CONH—, wherein R ₅₇ is an alkyl group (eg, each group such as methyl, ethyl, propyl, butyl, octyl, t-octyl, benzyl, etc.) and an alkenyl group (eg, allyl, octenyl,
It can represent an aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (eg, pyridinyl, pyrimidyl).

R ₅₄ is an alkyl group, a hydroxyl group,
Aryl group, an alkoxy group, represents an alkenyloxy group or an aryloxy group, these alkyl group, for the aryl group, alkyl group represented by R _51, there may be mentioned specifically those same aryl group ,or,
As for the alkoxy group, the aforementioned R ₅₂ , R ₅₃ , R ₅₅ and R ₅₆
And the same as the alkoxy group described for the above.

R ₅₁ and R ₅₂ may be closed with each other to form a 5- to 6-membered heterocyclic ring, and R ₅₃ and R ₅₄ may be closed with each other to form a 5-membered ring. These rings include those in which another ring is spiro-bonded.

Hereinafter, typical specific examples of the compound represented by the formula [A] will be shown, but the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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The compound represented by the general formula [A] is described in Journal of the Chemical Society (Journ).
al of the Chemical Society
y), 415-417 (1962), 2904-29
14 (1965); The Journal of Organic Chemistry (The Journal of Organic Chemistry)
rganic Chemistry), Volume 23, 75-
Page 76; Tetrahedron 2
6, 4743-4751 (1970); Chemical Letters (Chem., Lett.), (4), 315-3.
16 (1972); Journal of the Chemical Society of Japan, No. 10,19
87-1990 (1972); Bulletin of Chemical Society of Japan, 53, 5
It can be easily synthesized by the method described on pages 55 to 556 (1980).

[0047]

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In the general formula [B], R ₆₁ represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group or an aryl group, and R ₆₂ represents a halogen atom, an alkyl group, an alkenyl group. Represents a group, a cycloalkyl group or an aryl group, and r1 represents an integer of 0 to 3. When two or more R ₆₁ and R ₆₂ are each present in the compound, each R ₆₁ and R ₆₂ may be the same or different. Y ₁
Is -S -, - SO -, - represents a or an alkylene group - SO _2.

The secondary or tertiary alkyl group or the secondary or tertiary alkenyl group represented by R ₆₁ includes:
Those having 3 to 32 carbon atoms, particularly those having 4 to 12 carbon atoms are preferable, and specifically, t-butyl, sec-butyl, t-amyl, sec-amyl, t-octyl, i-propyl,
groups such as i-propenyl and 2-hexenyl.
Preferably has 1 to 32 carbon atoms as the alkyl group represented by R _62, the alkenyl group preferably has 2 to 32 carbon atoms, also may be linear or branched. Specifically, methyl, ethyl, t-butyl, pentadecyl, 1-hexylnonyl, 2-chlorobutyl, benzyl, 2,4-
And groups such as di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl, isopropenyl and the like.

[0050] As the cycloalkyl groups represented by R ₆₁ and R ₆₂ are preferably those having 3 to 12 carbon atoms, cyclohexyl, 1-methylcyclohexyl, and a group of cyclopentyl and the like.

The aryl group represented by R ₆₁ and R ₆₂ is preferably a phenyl or naphthyl group, and specifically, phenyl, 4-nitrophenyl, 4-t-butylphenyl,
2,4-di-t-amylphenyl, 3-hexadecyloxyphenyl, α-naphthyl and the like can be mentioned.

The alkylene group represented by Y ₁ is preferably one having 1 to 12 carbon atoms, specifically, methylene,
Examples include groups such as ethylene, propylene, butylene, and hexamethylene.

Each of the groups represented by R ₆₁ , R ₆₂ and Y ₁ may have a substituent. Examples of the substituent include a halogen atom and nitro, cyano, amide, sulfonamide, alkoxy, aryloxy , Alkylthio, arylthio, acyl and the like.

The following are typical examples of the general formula [B], but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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The compound represented by the general formula [B] is disclosed in US Pat. No. 2,807,653, Journal of the Chemical Society Parkin I (J. Chem. So.
c. Perkin I), page 1712 (1979).

The amount of the image stabilizer represented by the general formulas (A) and (B) is 5 to 40, respectively, based on the magenta coupler represented by the general formula (I) of the present invention.
It is preferably 0 mol%, more preferably 10 to 10 mol%.
250 mol%.

The magenta coupler of the present invention represented by the general formula (I) and the above-mentioned image stabilizer are preferably used in the same layer, but the image stabilizer is preferably contained in a layer adjacent to the layer where the coupler is present. May be used.

The magenta coupler of the present invention represented by the general formula (I) is usually used in an amount of 1 × 10 ^-3 per mol of silver halide.
mol to 8 × 10 ^-1 mol, preferably 1 × 10 ^-2 mol
It can be used in the range of ^{1 to} 8 × 10 ^-1 mol.

The magenta coupler represented by the general formula (I) of the present invention can be used in combination with another type of magenta coupler.

In order to incorporate the magenta coupler represented by the general formula (I) of the present invention, a conventional method, for example, a method using a known high-boiling solvent such as dibutyl phthalate or tricresyl phosphate, butyl acetate or ethyl acetate can be used. And the like. The magenta coupler represented by the general formula (I) is dissolved alone or in combination in a mixed solution of a low-boiling solvent or a solvent having only a low-boiling solvent, and then mixed with a gelatin aqueous solution containing a surfactant. Then, after emulsifying and dispersing using a high-speed rotary mixer, a colloid mill or an ultrasonic dispersing machine, a method of directly adding to the emulsion can be adopted. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

The magenta coupler represented by the general formula (I) of the present invention may be separately dispersed in a high boiling point solvent and the above-mentioned dispersion method and added to a silver halide emulsion.
A method in which both compounds are simultaneously dissolved, dispersed and added to the emulsion is preferred.

The amount of the high boiling point solvent to be added is preferably 0.01 to 10 g, more preferably 0.1 to 10 g, based on 1 g of the magenta coupler represented by the general formula (I) of the present invention.
It is in the range of 3.0 g.

As the silver halide emulsion used in the light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer. A coupler is used in an emulsion layer of a color photographic light-sensitive material.

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, and a coupling reaction with a colored coupler having a color correcting effect, a competitive coupler, and an oxidized form of a developing agent. Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material of the present invention may contain an image stabilizer and an ultraviolet absorber for the purpose of preventing the deterioration of the dye image.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, a generally known color photographic processing can be performed after exposure.

[0073]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Polyethylene was laminated on one side of a paper support and polyethylene oxide containing titanium oxide was laminated on the other side. On the support, each layer having the following constitution was replaced with a polyethylene layer containing titanium oxide. And a sample 101 of a multilayer silver halide color photographic light-sensitive material was prepared. The coating solution was prepared as follows.

First layer coating solution: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-1)
-2) 6.67 g, additive (HQ-1) 0.67 g, irradiation prevention dye (AI-3) 0.335 g, high boiling point organic solvent (DNP) 6.67 g and ethyl acetate 60 m
1 and dissolved, and this solution was added to a 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount added in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion)
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
The solution was added simultaneously over 30 minutes while controlling to 0, and the following (Solution C) and (Solution D) were further pAg = 7.3 and pH = 5.
5 and simultaneously added over 180 minutes. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For control of pAg, a control solution having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide. The ratio of chloride ion to bromide ion is 99.8: 0.2. When mixing the liquids, the molar ratio was 0.1 mol / l, and when mixing the liquids C and D, the molar ratio was 1 mol / l.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide Water was added to make up to 200 ml.

(Solution B) 10 g of silver nitrate was added to make up to 200 ml.

(Solution C) 102.7 g of sodium chloride 1.0 g of potassium bromide Water was added to make up to 600 ml.

(Solution D) Silver nitrate 300 g Water was added to make up to 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.85 μm, a variation coefficient of 0.07, and a silver chloride content of 99.5 mol. % Of a monodispersed cubic emulsion EMP-1.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a size of 3 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Method for Preparing Red-Sensitive Silver Halide Emulsion) (Solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodispersed cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol% was obtained. EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX The coefficient of variation is a number obtained by dividing the standard deviation of the particle size by the average particle size.

[0097]

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Next, Sample 10 was prepared except that the coupler M-1 in the third layer was replaced with an equimolar magenta coupler shown in Table 3 below, and the dye image stabilizer was changed as shown in Table 3.
Samples 102 to 119 were produced in the same manner as in No. 1.

The sample thus prepared was subjected to wedge exposure with green light by a conventional method, and then processed according to the following processing steps.

Processing Step Temperature Time Color Development 35.0 ± 0.3 ° C. 45 seconds Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds The composition of the treatment liquid is shown below.

The replenishment rate of each processing solution was 80 cc./m ^{2 of} silver halide color photographic light-sensitive material. It is.

Color developer tank liquid Replenisher Pure water 800 ml 800 ml triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g potassium chloride 2.4 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Fluorescent whitening agent (4,4′-diaminostilbenesulfonic acid derivative) 1.0 g 1. 8 g Potassium carbonate 27 g 27 g Water was added to make the total volume 1000 ml. The pH of the tank solution was 10.10, and the pH of the replenisher was 10.10.
Adjust to 60.

Bleaching / fixing solution (the tank solution and the replenisher are the same) Ethylenediaminetetraacetate ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml In addition, the total volume is made up to 1000 ml and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (the tank solution and the replenishing solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Fluorescent whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g Water is added to make the total volume 1000 ml, and sulfuric acid or water Adjust the pH to 7.0 with potassium oxide.

The following evaluation was performed using the sample after the continuous treatment.

<Dmax> The maximum color density was measured.

<Light Resistance> The obtained sample was irradiated with a xenon fade meter for 7 days, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined.

Table 3 shows the results.

[0109]

[Table 3]

[0110]

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As is evident from the results in Table 3, Sample 10
Sample No. 1 to 119 using the coupler of the present invention
5 to 114 are samples 102 and 1 using the comparative coupler.
A very large improvement in light resistance was observed as compared with that of No. 04.

Further, it was found that the effects of the samples 115 to 119 in which the dye image stabilizer was used in combination with the coupler of the present invention were further amplified.

In addition, it was also confirmed that the coupler of the present invention had improved coloring properties as compared with the comparative coupler.

[0114]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is excellent in color-forming properties and has remarkably improved light fastness of magenta dye images.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Fumio Ishii Konica Corporation, 1 Sakuracho, Hino City, Tokyo

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. A silver halide color photographic light-sensitive material, characterized in that at least one green-sensitive silver halide emulsion layer contains at least one magenta coupler represented by the following formula (I). Embedded image [Wherein, R ₁ represents a substituent, R ₂ represents a hydrogen atom, an alkyl group or an aryl group, and R ₃ represents an alkyl group, an aryl group, -CO ₂ R ₄ , -CONHR ₄ , -NHCOR ₄ ,-
_{NHCONHR 4, -NHR 4, -N (} R 4) 2, -S
Represents R ₄ , —SO ₂ R ₄ or —NHSO ₂ R ₄ , wherein R ₄ represents an alkyl group or an aryl group. The alkyl group and the aryl group may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ]