JP2000267237A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material excellent in color forming property and having remarkably improved light fastness of a magenta dye image by incorporating a specified magenta coupler into one of green-sensitive silver halide emulsion layers. SOLUTION: The silver halide photographic sensitive material has photographic constituent layers including blue-, green- and red-sensitive silver halide emulsion layers on a substrate and contains a magenta coupler of the formula in one of the green-sensitive silver halide emulsion layers. In the formula, R is H or a substituent, R1 and R2 are each alkyl, L1 is alkylene or arylene, L2 is alkylene, arylene, O, carbonyl, sulfonyl or a divalent group obtained by combining these, R3 and R4 are each H or a substituent, R5 is a substituent, (n) is an integer of 0-4, X is H or an atom or group which can be released by reaction with the oxidized body of a color developing agent and Z is a group of nonmetallic atoms required to form an N-containing heterocycle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a magenta coupler, and more particularly to a silver halide photographic light-sensitive material containing a novel pyrazolotriazole-based magenta coupler, which has excellent color developability, And a silver halide photographic light-sensitive material capable of obtaining a stable dye image.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as color photographic light-sensitive materials, light-sensitive materials), generally used couplers include yellow couplers composed of open-chain ketomethylene compounds, pyrazolone compounds, and pyrazolo compounds. Magenta couplers composed of azole compounds, phenolic compounds, cyan couplers composed of naphthol compounds and the like 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.
Pp. 41, pp. 108-110, Proceedings of the Photographic Society of Japan, Annual Meeting of 1985, pp. 108-110, the dyes formed from pyrazolone magenta couplers have undesirable side absorption, and improvement is desired. I was

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 is described in the above literature and US Pat. No. 3,725,067,
Nos. 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, 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, in any of the above techniques, 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 magenta dye image having excellent color fastness and markedly improved light fastness. An object of the present invention is to provide a silver halide color photographic light-sensitive material.

[0010]

The above object of the present invention is attained by the following constitutions.

1. In a silver halide 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, the green-sensitive silver halide emulsion A silver halide photographic material comprising at least one layer containing a magenta coupler represented by the following formula [M-1].

[0012]

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In the formula, R represents a hydrogen atom or a substituent.
R ₁ and R ₂ represent an alkyl group. L ₁ represents an alkylene group or an arylene group; L ₂ represents an alkylene group, an arylene group, an oxygen atom, a carbonyl group, a sulfonyl group, or a divalent group obtained by combining these. R ₃ and R ₄ represent a hydrogen atom or a substituent, and R ₅ represents a substituent. n
Represents an integer of 0 to 4. X represents an atom or a group which can be eliminated by a reaction with a hydrogen atom or an oxidized form of a color developing agent. Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring.

2. 2. The halogenation according to the above 1, wherein the green photosensitive silver halide emulsion layer contains at least one compound selected from the compounds represented by the following general formulas [A] and [B]. Silver photographic photosensitive material.

[0015]

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In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0017]

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[0018] represents a wherein _{R 21 a, R 21 b,} R 21 c is a monovalent organic group, respectively. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R
₂₆ represents a hydrogen atom, a halogen atom, or a group that can be substituted on a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- to 6-membered ring.

[0019]

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In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring together with a nitrogen atom.

Hereinafter, the present invention will be described in more detail.

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

In the general formula [M-1], the substituent represented by R is an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a 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 residue (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group , A pyrazolyl group, a tetrazolyl group, etc.), a halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), an alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, 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, butyloxycarbonyl 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.), sulfamoyl group (example) For example, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl ,
2-pyridylaminosulfonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group Etc.), an acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group,
Cyclohexylcarbonyl group, octylcarbonyl group,
2-ethylhexylcarbonyl 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, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (for example, Methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino Group, naphthylcarbonylamino group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group) 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,
Examples include a nitro group, a sulfo group, a carboxyl group, and a hydroxyl group. More preferred as R is an alkyl group, and particularly preferred is a tert-butyl group.

The alkyl groups represented by R ₁ and R ₂ include, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl And the like. Preferred among these groups is a methyl group.

Examples of the alkylene group represented by L ₁ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, an octylene group and a decylene group.

Examples of the arylene group represented by L ₁ include a phenylene group and a naphthalene group.

Of the groups represented by L ₁ , preferred are an ethylene group and an o-phenylene group, and more preferred is an ethylene group.

Examples of the alkylene group and arylene group represented by L ₂ include the same groups as L ₁ .

Among the groups represented by L ₂ , preferred are a carbonyl group, a sulfonyl group and a group represented by the following L2-a, more preferably a group represented by L2-a. R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group.

[0030]

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The substituents represented by R ₃ , R ₄ and R ₅ include the same groups as R.

Among the groups represented by R ₃ and R ₄ , preferred are a hydrogen atom, a carbonyl group and a sulfonyl group, and R ₃ and R ₄ are not simultaneously hydrogen atoms.

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 (a chlorine atom, a bromine atom, a fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples include acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded with an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl and the like, preferably a halogen atom, particularly preferably a chlorine atom.

The nitrogen-containing heterocyclic ring formed by Z includes a pyrazole ring, an imidazole ring, a triazole ring,
And a tetrazole ring. The skeleton represented by the general formula [M-1] is preferably the following Ma to Mf, and more preferable skeletons are Ma and Mb.
And Mc, and more preferably Ma.

[0035]

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The following are typical examples of the compound represented by the general formula [M-1] of the present invention, but the present invention is not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042] The pyrazoloazole-based magenta coupler of the present invention can be prepared by using the 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
No., Synthesis, 1981, p. 40, 198
4 years 122 pages, 1984 894 pages, JP-A-49-5
3574, British Patent 1,410,846, New Experimental 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 examples of the synthesis of the pyrazoloazole-based magenta coupler of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (9)

[0045]

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Compound (I) (5.2 g) was treated with ethyl acetate (20 m).
and 15 ml of water, and 1.8 g of potassium carbonate was added thereto. 2.4 g of compound (II) was added thereto over 10 minutes, and the mixture was further stirred for 1 hour. After removing the aqueous layer, the mixture was washed with water. Raney nickel was added to the organic layer and hydrogenated by a conventional method. After removing Raney nickel, ethyl acetate was removed by distillation under reduced pressure to obtain compound (IV). To this, 20 ml of THF and 0.9 g of pyridine were added to form a uniform solution, and 1.8 g of octanoyl chloride was added at room temperature for 10 minutes, followed by stirring for 1 hour. After removing THF under reduced pressure, 20 ml of ethyl acetate was added, and the mixture was washed with water and distilled off again under reduced pressure. The obtained fraction was purified by column chromatography (adsorbent: silica gel, developing solvent: ethyl acetate / hexane) to give Exemplified Compound (9).
3.7 g was obtained.

Synthesis Example 2 Synthesis of Exemplified Compound (11)

[0048]

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Compound (I) (5.2 g) was treated with ethyl acetate (20 m).
and 15 ml of water, and 1.8 g of potassium carbonate was added thereto. 2.4 g of compound (II) was added thereto over 10 minutes, and the mixture was further stirred for 1 hour. After removing the aqueous layer, the mixture was washed with water. Raney nickel was added to the organic layer and hydrogenated by a conventional method. After removing Raney nickel, ethyl acetate was removed by distillation under reduced pressure to obtain compound (IV). To this, 20 ml of THF and 0.9 g of pyridine were added to form a uniform solution, and 2.3 g of octanesulfonyl chloride was added at room temperature for 10 minutes and the mixture was further stirred for 1 hour. After removing THF under reduced pressure, ethyl acetate 20 was removed.
Then, the mixture was washed with water and distilled off under reduced pressure again. The obtained fraction was purified by column chromatography (adsorbent: silica gel, developing solvent: ethyl acetate / hexane) to obtain 3.9 g of Exemplified Compound (11).

The compounds synthesized above were identified by MASS,
It was confirmed by NMR and IR spectra that each was the target compound.

In the present invention, the silver halide emulsion layer containing the magenta coupler of the present invention may have the above general formula [A]
Alternatively, it is preferable that at least one compound selected from the compounds represented by [B] is contained.

In the general formula [A], the alkyl group represented by R ₂₁ preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R ₂₁ is preferably a phenyl group.

The heterocyclic ring represented by R ₂₁ is preferably a 5- to 7-membered heterocyclic ring, and specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidyl group and a 2-benzothiazolyl group.

[0055] The monovalent organic group represented by each of R ₂₁ a, R ₂₁ b and R ₂₁ c, an alkyl group, an aryl group,
Examples thereof include an alkoxy group, an aryloxy group, and a halogen atom. R ₂₁ is preferably a hydrogen atom or an alkyl group. The substituent groups on the benzene ring represented by each of R ₂₂ to R _26, is not particularly limited, typically alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl And other groups such as a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, acyloxy, alkylamino, imide, ureido, sulfamoyl amino,
Examples include alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and the like.

[0056] Each a is a hydrogen atom R _22, R _23, R ₂₅ and R _26, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, preferably an aryloxy group or an acylamino group, an alkyl group as R _24, hydroxy Groups, aryl groups, alkoxy groups or aryloxy groups are preferred. R ₂₁ and R ₂₂ may be closed with each other to form a 5- or 6-membered ring, in which case R ₂₄ is preferably a hydroxy group, an alkoxy group or an aryloxy group. R ₂₁ and R ₂₂
May be closed to form a methylenedioxy ring. Furthermore, R ₂₃ and R ₂₄ may be closed to form a 5-membered hydrocarbon ring, in which case R ₂₁ is preferably an alkyl group, an aryl group, or a heterocyclic group.

Specific examples of the compound represented by the general formula [A] are shown below.

[0058]

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In addition to the specific examples described above, specific examples of the compound represented by the general formula [A] include JP-A-60-262.
No. 159, page 11 to page 13, exemplary compounds A-1 to A-28, and No. 61-145552, page 8 to page 10, exemplary compounds PH-1 to PH-.
29, Exemplified compounds B-1 to B-21 and 2-958 described on pages 6 to 7 of JP-A-1-306846.
Compound I- described on pages 10 to 18 of JP-A No.
1 to I-13, I'-1 to I'-8, II-1 to II-1
2, II'-1 to II'-21, III-8 to III-14, IV-
1 to IV-24, V-13 to V-17, 3-39956
Compound II- described on pages 10 to 11 of JP-A No.
1 to II-33 and the like.

Next, in the general formula [B], R ₃₁ represents an aliphatic group or an aromatic group, preferably an alkyl group, an aryl group, or a heterocyclic group, and most preferably an aryl group. Examples of the heterocyclic ring formed by Y together with the nitrogen atom include a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1,1-dione ring,
And a pyrrolidine ring.

Specific examples of the compound represented by the formula [B] are shown below.

[0062]

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In addition to the specific examples described above, specific examples of the compound represented by the general formula [B] are described in JP-A-2-1675.
Illustrative Compound B described on pages 8 to 11 of JP-A-43
-1 to B-65, No. 4 of JP-A-63-95439.
Exemplary compounds (1) to (120) described on page 7 to page 7 can be exemplified.

The amount of the compound represented by the general formula [A] or [B] may be 5 to 5 parts with respect to the magenta coupler of the present invention.
~ 500 mol% is preferred, and more preferably 20 ~ 20 mol%.
0 mol%. Within the above range, the compound is 2
More than one species may be used in combination.

The magenta coupler represented by the general formula [M-1] 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 [M-1] of the present invention, a conventional method, for example, using a known solvent such as a high boiling solvent such as dibutyl phthalate or tricresyl phosphate and butyl acetate, Gelatin containing a surfactant after dissolving the magenta coupler represented by the general formula [M-1] alone or in combination in a mixture of low-boiling solvents such as ethyl acetate or a solvent containing only low-boiling solvents, or A method of mixing with an aqueous solution, then emulsifying and dispersing using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then directly adding the mixture 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 of the present invention represented by the general formula [M-1] may be separately dispersed in a high-boiling solvent and the above-mentioned dispersion method and added to a silver halide emulsion. A method of dissolving and dispersing at the same time and adding to the emulsion is preferred.

The amount of the high boiling 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 [M-1] of the present invention.
Ｇ3.0 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.

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

[0076]

EXAMPLES The present invention will be specifically described below with reference to examples, but embodiments of the present invention are not limited thereto.

On a support in which polyethylene is laminated on one side of a paper support and polyethylene containing titanium oxide is laminated on the other side, each layer having the following constitution is placed on the side of the polyethylene layer containing titanium oxide. Sample 1 of a multi-layer silver halide color photographic light-sensitive material was prepared by coating. The coating solution was prepared as follows.

First Layer Coating Solution Yellow Coupler (EY-
1) 26.7 g, dye image stabilizer (ST-1)
0g, dye image stabilizer (ST-2) 6.67g, additive (HQ-1) 0.67g, irradiation prevention dye (AI-3), high boiling point organic solvent (DNP) 6.67g and ethyl acetate 60 ml was added and dissolved, and this solution was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) 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-1) was added to the second and fourth layers, and (H-2) was 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.

[0081]

[Table 1]

[0082]

[Table 2]

The amounts of silver halide emulsions are shown in terms of silver.

[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% gelatin aqueous 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, and the concentration of the control solution is (solution A). , (Liquid B) and 0.1 mol / L when mixing (Liquid C) and (Liquid D).

(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 made up to 200 ml by adding water (Solution C) 102.7 g of sodium chloride 1.0 g of potassium iodide was added to make up to 600 ml with water (Solution D) 300 g of silver nitrate was added to make up to 600 ml with water. After desalting, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.8.
A monodispersed cubic emulsion EMP-1 having a thickness of 5 μm, a coefficient of variation (σ / F) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

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 for green-sensitive silver halide emulsion) Addition time of (Solution A) and (Solution B) and the time of (Solution C) and (Solution D) A monodisperse cubic emulsion EMP- having an average particle size of 0.43 μm, a coefficient of variation (σ / F) = 0.08, and a silver chloride content of 99.5 mol% in the same manner as in EMP-1 except that the addition time was changed. 2 was obtained.

EMP-2 was prepared by using the following compound.
Chemical ripening was performed at 5 ° C. for 120 minutes 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 monodisperse cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was prepared by using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes 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

[0098]

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The coefficient of variation is calculated from the standard deviation (σ) and the average particle size (γ).

[0100]

(Equation 1)

Γ ₁ represents the particle size, and n ₁ represents the number of particles having a particle size of γ ₁ .

Next, in Sample 1, the comparative coupler 1 in the third layer was replaced with the coupler shown in Table 3 (the amount added was the same molar amount as that of the comparative coupler 1), and the dye image stabilizer was further modified as shown in Table 3. Except that the sample was replaced,
~ 16 were produced.

The obtained sample was exposed to wedges according to a conventional method, developed, and measured for Dmax and light resistance of the green-sensitive photosensitive layer.

The light resistance was measured by irradiating the obtained sample with sunlight for 16 days and determining the residual rate (%) of the dye image at an initial density of 1.0. The results are summarized in Table 3.

[0105]

[Table 3]

As is evident from the results in Table 3, the samples using the coupler of the present invention all have higher Dmax and are superior in color developing property as compared with the samples using the comparative coupler 1.

Also, among Samples 1 to 11, Samples 2 to 11 using the coupler of the present invention are superior in color development and light resistance as compared with Sample 1 using the comparative coupler. I understand. In addition, it can be seen that when the dye image stabilizer of the present invention is used in combination, the image obtained from the coupler of the present invention can obtain more excellent light fastness.

[0108]

As demonstrated in the examples, the silver halide photographic light-sensitive material according to the present invention is excellent in color developability, and the light fastness of a magenta dye image is remarkably improved, so that an excellent image can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyuki Yasukawa 1st Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house F-term (reference) 2H016 BD05 BE03 BF06 BG02 BM07

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising a support having thereon 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. A silver halide photographic material comprising a magenta coupler represented by the following formula [M-1] in at least one of the light-sensitive silver halide emulsion layers. Embedded image [Wherein, R represents a hydrogen atom or a substituent. R ₁ and R ₂ represent an alkyl group. L ₁ represents an alkylene group or an arylene group; L ₂ represents an alkylene group, an arylene group, an oxygen atom, a carbonyl group, a sulfonyl group, or a divalent group obtained by combining these. R ₃ and R ₄ represent a hydrogen atom or a substituent, and R ₅ represents a substituent. n represents an integer of 0 to 4. X represents an atom or a group which can be eliminated by a reaction with a hydrogen atom or an oxidized form of a color developing agent. Z represents a nonmetallic atom group necessary to form a nitrogen-containing heterocyclic ring. ] 2. The green light-sensitive silver halide emulsion layer contains at least one compound selected from the compounds represented by the following general formulas (A) and (B). 2. The silver halide photographic light-sensitive material according to item 1. Embedded image [Wherein, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or the following residue. Embedded image Wherein _{R 21 a, R 21 b,} R 21 c represents a monovalent organic group, respectively. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, a halogen atom or a group which can be substituted on a benzene ring. R _{21 to} R ₂₆ are mutually bonded to form
A 6-membered ring may be formed. [Formula 4] [In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring together with a nitrogen atom. ]