JPH09311424A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material excellent in coloring property and giving a magenta dye image having remarkably improved light fastness. SOLUTION: This silver halide color photographic sensitive material has photographic constituent layers including blue-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers and red-sensitive silver halide emulsion layers on the substrate and contains at least one kind of coupler represented by formula (M-1) in at least one of the green-sensitive silver halide emulsion layers. In the formula I, R1 is H or a substituent, R2 is phenylene or alkylene, R3 is a monovalent >=15C nonarom. org. group having two or more hydroxyl groups, L is a divalent combining group, X is H or an atom or a group releasable by reaction with the oxidized body of a color developing agent and Z is a group of nonmetallic atoms required to form an N-contg. hetero ring.

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, and more particularly, to containing a novel pyrazolotriazole-based magenta coupler to provide excellent color reproducibility and coloring. Further, the present invention relates to a silver halide color photographic material capable of obtaining a dye image stable to heat and light.

[0002]

BACKGROUND OF THE INVENTION In silver halide color photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials), the couplers generally used are yellow couplers composed of open chain ketomethylene compounds, pyrazolone compounds and pyrazoloazole compounds. Cyan couplers composed of magenta couplers, phenol compounds and naphthol 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-mentioned literature, the dye formed from the pyrazoloazole type magenta coupler has no side absorption. The fact that this coupler is a good coupler is described in the above-mentioned documents in U.S. Pat. Nos. 3,725,067, 3,758,309 and 3,810,761.

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, research has been conducted to improve 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
No. 63-163351 discloses a technique of using an amine compound in combination.

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

However, also in the above technique, the fastness to light of a 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 object of the present invention is achieved by the following constitution.

1. In a silver halide color photographic light-sensitive material having a photographic constituent 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, said green-sensitive silver halide A silver halide color photographic light-sensitive material characterized in that at least one of the emulsion layers contains at least one coupler represented by the following formula (M-1).

[0012]

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In the formula, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a phenylene group or an alkylene group. R ₃ represents a monovalent non-aromatic organic group containing two or more hydroxyl groups and having a total carbon number of 15 or more. L is 2
Represents a valent linking group. X represents a hydrogen atom or an atom or group capable of leaving by reaction with an oxidized product of a color developing agent, and Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle.

The present invention will be described in detail below.

The magenta coupler represented by the general formula (M-1) of the present invention will be described.

In the general formula (M-1), the substituent atom or substituent represented by R ₁ is an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group). Group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, Naphthyl group, etc., heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, Tetrazolyl group etc.), halogen atom (eg chlorine atom, bromine atom, iodine) Child, such as a fluorine atom), an alkoxy group (e.g., methoxy group, ethoxy group, propyloxy group, a pentyloxy group, cyclopentyloxy group,
Hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), alkoxycarbonyl group (eg methyloxycarbonyl group, ethyloxycarbonyl group, butyl) Oxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group) , Butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc.), Famoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl group Aminosulfonyl group, 2-pyridylaminosulfonyl group and the like), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2 -Pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group) Group, octyl group, 2-ethylhexyl group,
Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group) Group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (for example, methylcarbonylamino group, ethylcarbonylamino) Group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexyl group Sill aminocarbonyl group, octylaminocarbonyl group, a dodecyl aminocarbonyl group,
Phenylaminocarbonyl group, naphthylaminocarbonyl group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group) , 2-pyridylsulfonyl group, etc.),
Amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group,
Anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group and the like, and these groups may be further substituted by the above-mentioned substituents. .

Of these, for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, Each group such as carboxyl is preferred, more preferred is an alkyl group, and particularly preferred is a t-butyl group.

Examples of the alkylene group represented by R ₂ include methylene group, ethylene group, dimethylethylene group, propylene group, isopropylene group, butylene group and the like.

Examples of the arylene group represented by R ₂ include a phenylene group and a naphthalene group.

Preferred as R ₂ is an alkylene group.

As the divalent linking group represented by L, for example,
Examples thereof include an oxygen atom, a carbonyl group, a carbonyloxy group, a carboxamide group, a sulfonamide group, an alkylene group, a phenylene group, and a group in which these are combined.

Examples of the group represented by R ₃ include the following general formulas [I] to [VI].

[0023]

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In the general formulas [I] to [VI], R
₁₀ represents a simple bond, a hydrogen atom, or an acyl group.
However, at least two of the groups represented by R ₁₀ are hydrogen atoms. n represents an integer of 1 to 5.

These groups may further have a substituent, and examples of the substituent include the same groups as R ₁ .

Examples of the atom and group which can be eliminated by the reaction with the oxidation product of the color developing agent represented by X include halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing N-bonded Examples thereof include heterocyclic groups, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and other groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring. Among these, preferable skeletons are A, B and C described below, and more preferably A.

[0028]

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The typical examples of the magenta coupler represented by formula (M-1) of the present invention are shown below, but the present invention is not limited thereto.

[0030]

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[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

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[0034]

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[0035]

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[0036]

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The above-mentioned pyrazoloazole-based magenta coupler of the present invention is a Journal of the Chemical Society (Journal of the Chemical).
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
Issue, Synthesys, 1981, p. 40, ibid. 198.
4 pages, 122 pages, 1984 pages, 894 pages, JP-A-49-5.
No. 3574, British Patent 1,410,846, New Laboratory Chemistry Course 14-III, pp. 1585 to 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.

Next, typical synthesis examples of the pyrazoloazole-based magenta coupler of the present invention are shown below.

Synthesis Example 1 << Synthesis of Exemplified Compound (2) >>

[0040]

[Chemical 12]

6 g of toluene was added to 12 g of (I) and 5 g of succinic anhydride, and the mixture was heated at 80 to 100 ° C. for 4 hours. 30 ml of ethyl acetate was added, washed with water and concentrated. The residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate, n-hexane) to obtain (II) 12 g. This was dissolved in 60 ml of acetonitrile, 4 ml of acetic anhydride and 2.6 ml of pyridine were added, and the mixture was heated under reflux for 1.5 hours. After concentrating the reaction solution, 60 ml of ethyl acetate was added, washed with water and concentrated. The residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate, n-hexane) to obtain (III) 4g. To this, 30 ml of chloroform and 2.4 ml of thionyl chloride were added, stirred at room temperature for 2 hours, and concentrated. Next, 4.3 g of (IV) and 1 g of pyridine were dissolved in 30 ml of ethyl acetate, and a solution of the residue in 5 ml of ethyl acetate was added thereto over 30 minutes, and the mixture was heated at 40 to 50 ° C. for 1 hour. After washing with water, 2.6 ml of 29% aqueous ammonia was added, and the mixture was heated at room temperature for 2 hours, washed with water and concentrated. The residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate, n-hexane) to obtain 3.3 g of oily exemplary compound (2).

Identification was carried out by MASS and NMR spectra, and it was confirmed that the compound was Exemplified compound M-6.

The magenta coupler represented by the general formula (M-1) of the present invention can be used in combination with the image stabilizer represented by the following general formula [A] and / or general formula [B].

[0044]

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In the general formula [A], R ₂₁ 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 ₂₁ includes, for example, allyl, hexenyl, octenyl and the like. Examples of the aryl group for R ₂₁ include phenyl and naphthyl groups. Further, examples of the heterocyclic group represented by R ₂₁ include tetrahydropyranyl and pyrimidyl groups. Each of these groups represented by R ₂₁ includes those having a substituent.

R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ 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. For the group and the aryl group, the alkyl group described for R ₂₁ 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, methoxy,
Specific examples thereof include ethoxy and benzyloxy groups. The acylamino group is represented by R ₂₇ CONH-
₂₇ is an alkyl group (for example, each group such as methyl, ethyl, propyl, butyl, octyl, t-octyl, and benzyl),
It can represent an alkenyl group (eg, groups such as allyl, octenyl, oleyl, etc.), an aryl group (eg, groups such as phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (eg, groups such as pyridinyl, pyrimidyl).

R ₂₄ 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 _21, there may be mentioned specifically those same aryl group ,or,
As for the alkoxy group, the aforementioned R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆
And the same as the alkoxy group described for the above.

R ₂₁ and R ₂₂ may be ring-closed to each other to form a 5- or 6-membered heterocycle, and R ₂₃ and R ₂₄ may be ring-closed to form a 5-membered ring. , These rings also include those in which another ring is spiro-bonded.

Typical specific examples of the compound represented by the above general formula [A] are shown below, but the present invention is not limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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The compound represented by the general formula [A] is a compound of 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).

[0056]

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In the general formula [B], R ₃₁ represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group or an aryl group, and R ₃₂ represents a halogen atom, an alkyl group or an alkenyl group. Represents a group, a cycloalkyl group or an aryl group, and n2 represents an integer of 0 to 3. When two or more R ₃₁ and R ₃₂ are present in the compound, each R ₃₁ and R ₃₂ may be the same or different. Y ₁
Is -S -, - SO -, - represents a or an alkylene group - SO _2.

As the secondary or tertiary alkyl group represented by R ₃₁ or the secondary or tertiary alkenyl group,
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.

The alkyl group represented by R ₃₂ preferably has 1 to ₃₂ carbon atoms, and the alkenyl group preferably has 2 to ₃₂ carbon atoms, and may be linear or branched. Specifically, groups such as methyl, ethyl, t-butyl, pentadecyl, 1-hexylnonyl, 2-chlorobutyl, benzyl, 2,4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl and isopropenyl Is mentioned.

The cycloalkyl group represented by R ₃₁ and R ₃₂ preferably has 3 to 12 carbon atoms, and examples thereof include cyclohexyl, 1-methylcyclohexyl and cyclopentyl groups.

The aryl group represented by R ₃₁ and R ₃₂ is preferably a phenyl group or a naphthyl group, 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 ₃₁ , R ₃₂ and Y ₁ may have a substituent, and examples of the substituent include a halogen atom and nitro, cyano, amido, sulfonamide, alkoxy and aryloxy. And groups such as alkylthio, arylthio, acyl and the like.

Typical examples of the general formula [B] are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

[Chemical 21]

The compound represented by the general formula [B] is represented by 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 formula [A] and the general formula [B] used is the same as that of the general formula (M-
For the magenta coupler shown in 1), 5
It is preferably from 400 to 400 mol%, more preferably from 10 to 250 mol%.

The magenta coupler represented by formula (M-1) of the present invention and the image stabilizer are preferably used in the same layer, but the image stabilizer is provided in the layer adjacent to the layer in which the coupler is present. You may use an agent.

The magenta coupler represented by formula (M-1) of the present invention is usually 1 × 10 ^-3 m ³ per silver halide.
ol-8 × 10 ^-1 mol, preferably 1 × 10 ^-2 mol
It can be used in the range of up to 8 × 10 ⁻¹ mol.

The magenta coupler represented by formula (M-1) of the present invention can be used in combination with other types of magenta couplers.

In order to incorporate the magenta coupler represented by the general formula (M-1) of the present invention, a conventional method, for example, a known high-boiling solvent such as dibutyl phthalate, tricresyl phosphate and butyl acetate, The magenta coupler represented by the general formula (M-1) is dissolved alone or in combination in a mixed solution of a low boiling point solvent such as ethyl acetate or a solvent having only a low boiling point solvent, and then a surfactant is added. A method of mixing with an aqueous gelatin solution, then emulsifying and dispersing using a high speed rotating mixer, a colloid mill or an ultrasonic disperser, and then directly adding to the emulsion can be adopted. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

The magenta coupler represented by the general formula (M-1) of the present invention may be separately dispersed in the high boiling point solvent and the above dispersion method and added to the silver halide emulsion. A method of simultaneously dissolving, dispersing and adding to the emulsion is preferable.

The amount of the high boiling point solvent added is preferably 0.01 to 10 g, more preferably 0.1 to 1 g of the magenta coupler represented by the general formula (M-1) of the present invention.
The range is up to 3.0 g.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary 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.

Antifoggants, stabilizers 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 may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly 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, a color coupler, a competing coupler and a developing agent, which have an effect of color correction, through a coupling reaction with an oxidized product. Compounds that release photographically useful fragments such as hardeners, antifoggants, 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.

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

[0083]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

Example 1 On a support having a polyethylene support laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, titanium oxide was applied to each layer having the constitution shown in Tables 1 and 2 below. By coating on the side of the contained polyethylene layer, a multilayer color photographic light-sensitive material sample 101 was prepared.

[0085]

[Table 1]

[0086]

[Table 2]

The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (S
T-2) 6.67 g, stain inhibitor (HQ-1) 0.
60 g of ethyl acetate was added to and dissolved in 67 g of 6.67 g of a high boiling point organic solvent (DNP), and the solution was dissolved in 220 cc of a 10% aqueous gelatin solution containing 7 cc of a 20% aqueous surfactant (SU-2) solution using an ultrasonic homogenizer. This was emulsified and dispersed to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an irradiation preventing dye (AIY-1) was further added to prepare a coating solution for the first layer.

The second to seventh layer coating solutions were prepared in the same manner as the first layer coating solution. (HH-1) was added to the second and fourth layers as a hardener, and (HH-2) was added to the seventh layer. Surfactants (SU-1), (SU-
3) was added to adjust the surface tension.

The structural formulas of the compounds used in the above layers are shown below.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

[Chemical formula 26]

The silver halide emulsions used in the first, third and fifth layers are as follows.

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.85 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% Sodium thiosulfate 0 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-21 × 10 ⁻⁴ mol / mol AgX green-sensitive silver halide emulsion (Em-G) monodisperse cubic silver chlorobromide having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol%. Emulsion 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 Red-sensitive Silver halide emulsion (Em R) Monodisperse cubic silver chlorobromide emulsion having an average particle size of 0.50 µm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / Molar AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0099]

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Next, the coupler EM- of the third layer of Sample 101 was used.
Same as Sample 101, except that 1 was replaced by the coupler of the present invention shown in Table 3 below or the coupler for comparison shown in an equimolar amount to the amount of coupler EM-1 added, and the dye image stabilizer was changed as shown in Table 3. Samples 102 to 118 were manufactured.
The structural formula of the magenta coupler EM-2 used for the comparative sample is shown together with EM-1 described above.

Each of the samples thus prepared was wedge-exposed with green light according to a conventional method, and then processed according to the following processing steps.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds The composition of each treatment liquid is shown below. The replenishment amount of each processing solution is 80 cc per m ^{2 of the} color photographic light-sensitive material.

Color developing solution Tank solution Replenishing solution Pure water 800 cc 800 cc 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 Optical brightener (4,4′-diaminostilbenedisulfonic acid derivative) 1.0 g 1 2.8 g potassium carbonate 27 g 27 g Water is added to bring the total amount to 1000 cc, and the pH is adjusted to 10.10 in the tank solution and 10.60 in the replenisher.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc Ammonium sulfite (40% aqueous solution) 27.5 cc Water In addition, the total amount is adjusted to 1000 cc, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid (tank liquid and replenishing liquid 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 0.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water was added to make the total amount 1000 cc, and sulfuric acid or water was added. Adjust the pH to 7.0 with potassium oxide.

The following evaluations were 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 10 days, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined.

The results are shown in Table 3.

[0110]

[Table 3]

As is clear from Table 3, samples 101 to 1
18, the sample 103 using the coupler of the present invention
Reference numeral 118 denotes samples 101 and 102 using the coupler for comparison.
It was confirmed that the light resistance was remarkably improved as compared with.

Further, it was also confirmed that the coupler of the present invention has a color forming property equivalent to or higher than that of the comparative coupler.

[0113]

The silver halide color photographic light-sensitive material according to the present invention has an excellent effect in that it is excellent in color developability and the light fastness of a magenta dye image is remarkably improved.

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 layer of the green-sensitive silver halide emulsion layer contains at least one kind of coupler represented by the following formula (M-1). Embedded image [In the formula, R ₁ represents a hydrogen atom or a substituent, and R _1
2 represents a phenylene group or an alkylene group. R ₃ represents a monovalent non-aromatic organic group containing two or more hydroxyl groups and having a total carbon number of 15 or more. L represents a divalent linking group. X represents a hydrogen atom or an atom or group capable of leaving by reaction with an oxidized product of a color developing agent, and Z represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle. ]