JPH1138569A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide color photographic sensitive material superior in color development performance and remarkably enhanced in the lightfastness of a magenta dye image by incorporating a specified magenta coupler in a green-sensitive silver halide emulsion layer. SOLUTION: At least one of the green-sensitive silver halide emulsion layers of this photosensitive material contains at least one of the magenta couplers represented by the formula sensitive material in which R1 is a substituent; R2 is an optionally substituted alkyl or cycloalkyl or aryl group; X1 is an H atom or a group to be released by reaction with the oxidation product of a color developing agent: Z1 is a non-metallic atomic group necessary to form a cyclic hydrocarbon or hetero ring; and X2 is a >C=O car >S(=O)2 .

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 present invention contains a novel pyrazoloazole type magenta coupler to provide excellent coloring properties, and furthermore to provide heat and light. The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a stable dye image with respect to light.

[0002]

2. Description of the Related Art In silver halide color photographic materials, couplers generally used include yellow couplers composed of open-chain ketomethylene compounds, magenta couplers composed of pyrazolone compounds and pyrazoloazole compounds, phenol compounds and naphthol compounds. Cyan couplers composed of compounds are known. Conventionally, 5-
Pyrazolone compounds are often used as magenta couplers.

Known pyrazolone magenta couplers include US Pat. Nos. 2,600,788 and 3,519,4.
No. 29, JP-A-49-111631, 57-358
No. 58, etc. However, the Theory of the Photographic Process (The Th
eory of the PhotographicP
process), Macmillan, 4th edition (1977), 3
56-358, Fine Chemicals, CMC Company, vol. 14, No. 8, pages 38-41, as summarized in the Photographic Society of Japan, 1985 Annual Meeting Abstracts, pp. 108-110. Dyes formed from pyrazolone magenta couplers have an undesirable side absorption, and improvement thereof is desired.

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-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, 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 object of the present invention is achieved by the following constitution.

(1) A silver halide color photographic light-sensitive material having a photographic component layer including 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 comprising at least one magenta coupler represented by the following formula (M-1) in at least one of the green-sensitive silver halide emulsion layers.

[0012]

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[In the formula, R ₁ represents a substituent, and R ₂ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. X ₁ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. Z ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. Z
₂ represents a group of nonmetallic atoms necessary for forming a cyclic hydrocarbon or a heterocyclic ring, and X ₂ represents> C ＝ O or> S (＝ O) ₂
Represents Hereinafter, the present invention will be described in detail.

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

In the general formula (M-1), the substituent represented by R ₁ is an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert group).
-Butyl group, pentyl 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 (eg, pyridyl group, thiazolyl group, oxazolyl group) , Imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, iodine atom, A fluorine atom), an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, an octyloxy group, a dodecyloxy group, etc.), an aryloxy group ( For example, phenoxy group, naphthyl An alkoxycarbonyl group (eg, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, a dodecyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, a phenyloxycarbonyl group, Naphthyloxycarbonyl group, etc.), sulfonamide group (for example, methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group,
Dodecylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group) , A dodecylaminosulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, a 2-pyridylaminosulfonyl group, etc., a ureido group (for example, a methylureido group, an ethylureido group, a pentylureido group, a 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, 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, 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. May be substituted by a group.

Among them, for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, acyloxy, amino,
Preferred are groups such as alkylamino, ureido, alkoxycarbonyl, aryloxycarbonyl, carboxyl and the like, more preferred are alkyl groups, and particularly preferred are t-butyl groups.

In the general formula (M-1), R ₂ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.

The alkyl group represented by R ₂ is preferably an alkyl group having 1 to 32 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, hexyl group, octyl group, dodecyl group. , Hexadecyl group, 2-ethylhexyl group and the like.

When the alkyl group represented by R ₂ has a substituent, examples of the substituent include the same groups as R ₁ in formula (M-1).

The cycloalkyl group represented by R ₂ is preferably a cycloalkyl group having 3 to 12 carbon atoms, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 2-hexyl group.
Methylcyclopropyl group, adamantyl group and the like are mentioned as typical examples.

When the cycloalkyl group represented by R ₂ has a substituent, the substituent is represented by the general formula (M-
The same groups as R ₁ in 1) can be mentioned.

The aryl group represented by R ₂ preferably has 6 to 14 carbon atoms, and typical examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

When the aryl group represented by R ₂ has a substituent, examples of the substituent include the same groups as those of R ₁ in formula (M-1).

In the general formula (M-1), the cyclic hydrocarbon or heterocyclic ring formed by Z ₂ includes a benzene ring, a pentalene ring, an indene ring, a naphthalene ring, an anthracene ring, a chrysene ring, a cyclohexene ring, and a pyridyl ring. Ring, thiazole ring, oxazole ring, imidazole ring, furan ring, thiophene ring, pyrrole ring, pyrazine ring, pyrimidine ring, pyridazine ring, pyrrolidine ring, pyrroline ring, imidazolidine ring, quinuclidine ring, indole ring, quinoline ring and the like. Can be

[0025] are shown below, but typical examples of the cyclic hydrocarbon or heterocyclic ring represented by Z _2, Z ₂ is not limited thereto.

[0026]

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In the general formula (M-1), Z ₂ is preferably a substituted or unsubstituted benzene ring, particularly preferably an ortho-substituted benzene ring.

In the general formula (M-1), X ₂ represents>
Represents C = O or> S (= O) ₂ .

In the general formula (M-1), the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₁ includes, 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, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl And the like, preferably a halogen atom, particularly a chlorine atom.

In the general formula (M-1), the nitrogen-containing heterocyclic ring formed by Z ₁ is a pyrazole ring,
Examples thereof include an imidazole ring, a triazole ring, and a tetrazole ring. Of these, preferred skeletons are the following [I] and [II], and more preferably [I].

[0031]

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Hereinafter, typical specific examples of the magenta coupler represented by formula (M-1) of the present invention will be shown, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040] The pyrazoloazole-based magenta coupler of the present invention can be prepared by using 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
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.

The following is a typical synthesis example of the magenta coupler represented by the general formula (M-1) of the present invention.

Synthesis Example 1 << Synthesis of Exemplified Compound M-1 >>

[0043]

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To 20.0 g of compound [A], 11.18 g of 2-aminobenzoic acid and 29.6 g of p-toluenesulfonic acid.
g and 300 ml of toluene were added, and the mixture was heated under reflux for 4 hours while distilling off the generated water. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated solid was filtered. By sequentially washing the obtained solid with ethyl acetate and water,
25.4 g of a white solid compound [B] was obtained.

3.29 g of the compound [B] obtained above
Into 20 ml of ethyl acetate and 1.01 g of potassium carbonate
Was dissolved in 10 ml of water. Further, a solution prepared by dissolving 2.31 g of the compound [C] in 4 ml of ethyl acetate was slowly dropped while vigorously stirring the mixture. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours to complete the reaction. After completion of the reaction, the aqueous layer was removed, and the obtained organic layer was washed three times with a saline solution. Ethyl acetate as a solvent was distilled off under reduced pressure, and the obtained residue was recrystallized from a mixed solvent of ethyl acetate / acetonitrile to give Exemplified Compound (M-1) 3.3 as a white solid.
9 g were obtained.

Identification was performed by MASS and NMR spectra, and it was confirmed that it was the illustration compound M-1.

Synthesis Example 2 << Synthesis of Exemplified Compound M-9 >>

[0048]

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To 2.81 g of the compound [B], 30 ml of acetonitrile and 1.36 ml of triethylamine were added. 2.09 g of compound [D] was slowly added thereto,
After completion of the addition, the mixture was stirred at room temperature for 5 hours to complete the reaction. After completion of the reaction, 50 ml of ethyl acetate and 50 ml of water were added to the reaction solution. After removing the aqueous layer, the obtained organic layer was washed successively with a dilute aqueous hydrochloric acid solution, a dilute aqueous sodium hydrogen carbonate solution and a saline solution. Ethyl acetate as a solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane) to give a light yellow oil of the exemplified compound (M-9). )
2.96 g were obtained.

Identification was carried out by MASS and NMR spectra, and it was confirmed that the compound was Exemplified Compound M-9.

The magenta coupler of the present invention represented by formula (M-1) is used in combination with an image stabilizer represented by the following formula [AO-I] and / or [AO-II]. be able to.

[0052]

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In the formula, R ₁₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0054]

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Here, R _121a , R _121b and R _121c each represent a monovalent organic group. R ₁₂₂ , R ₁₂₃ , R ₁₂₄ , R
Each of ₁₂₅ and R ₁₂₆ represents a hydrogen atom, a halogen atom, or a group that can be substituted on a benzene ring. Also, R _{121 to} R
₁₂₆ may combine with each other to form a 5- to 6-membered ring.

[0056]

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In the formula, R ₁₃₁ 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.

In the general formula [AO-I], R ₁₂₁
Examples of the alkyl group, aryl group, and heterocyclic group represented by are the groups described as an alkyl group or an aryl group represented by R ₂ or the like in the general formula [I], and examples of the heterocyclic group include a pyrazole group, -Imidazolyl group, 3-pyridyl group, 2-furyl group and the like. Also, R ₁₂₁ a,
R ₁₂₁ b, as the monovalent organic group represented by R ₁₂₁ c, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
And a halogen atom. R ₁₂₁ is preferably a hydrogen atom or an alkyl group. Examples of the group that can be substituted on the benzene ring represented by R _{122 to} R ₁₂₆ include a substituent when the alkyl group, aryl group, or the like represented by R ₂ or the like in the general formula [I] is further substituted. And the groups described above. R ₁₂₂ , R ₁₂₃ , R ₁₂₅ , and R ₁₂₆ are preferably a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an acylamino group, and R ₁₂₄ is an alkyl group, a hydroxy group, an aryl group,
Alkoxy groups and aryloxy groups are preferred. Also R
₁₂₁ and R ₁₂₂ may be closed with each other to form a 5- or 6-membered ring, in which case R ₁₂₄ is preferably a hydroxy group, an alkoxy group, or an aryloxy group. R ₁₂₁ and R ₁₂₂ may be closed to form a methylenedioxy ring. Furthermore, R ₁₂₃ and R ₁₂₄ may be closed to form a 5-membered hydrocarbon ring, in which case R ₁₂₁ is preferably an alkyl group, an aryl group, or a heterocyclic group.

Specific examples of the compound represented by the general formula [AO-I] are shown below.

[0060]

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[0061]

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In addition to the specific examples described above, the above general formula [AO-
Specific examples of the compounds represented by the formula (I)
Exemplified compounds A-1 to A-28 described on pages 11 to 13 of JP-A-262159 and Exemplified compounds PH-1 described on pages 8 to 10 of JP-A-61-145552.
PH-29, from page 6 of JP-A-1-306846
Exemplified compounds B-1 to B-21, 2-
Exemplified Compounds I-1 to I-13, I'-1 to I'-8, and II-1 to 958 described on pages 10 to 18 of JP-A-958
II-12, II'-1 to II'-21, III-8 to III-1
4, IV-1 to IV-24, V-13 to V-17, 3-3
Exemplary compounds II-1 to II-33 described on pages 10 to 11 of JP-A-9956 can be exemplified.

Next, in the general formula [AO-II],
R ₁₃₁ 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, a pyrrolidine ring and the like.

Specific examples of the compound represented by the general formula [AO-II] are shown below.

[0065]

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In addition to the specific examples described above, the above-mentioned general formula [AO-
Illustrative examples of the compound represented by the formula [II]
Illustrative compounds B-1 to B-65 described on pages 8 to 11 of JP-A-67543, and illustrative compounds (1) to (12) described on pages 4 to 7 of JP-A-63-95439.
0) and the like.

The general formula [AO-I] and the general formula [AO
-II], the amount of the image stabilizer used is based on the magenta coupler represented by formula (M-1) of the present invention.
The content is preferably 5 to 400 mol%, more preferably 10 to 250 mol%.

The magenta coupler represented by formula (M-1) of the present invention and the above-mentioned image stabilizer are preferably used in the same layer, but the image stabilizing agent may be contained in a layer adjacent to the layer where the coupler is present. An agent may be used.

The magenta coupler of the present invention represented by formula (M-1) is usually 1 × 10 ^-3 m per silver halide.
ol to 8 × 10 ^-1 mol, preferably 1 × 10 ^-2 mol
It can be used in the range of ８8 × 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, using a known solvent such as a high boiling solvent such as dibutyl phthalate or tricresyl phosphate and butyl acetate, 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 having only a low-boiling solvent, a surfactant is contained. A method of mixing with an aqueous gelatin solution, emulsifying and dispersing the mixture using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser, and then directly adding the resulting mixture to the emulsion can be employed. 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 formula (M-1) 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 of dissolving, dispersing, and adding to the emulsion simultaneously is preferable.

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 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, by a coupling reaction with a colored coupler having a color correction 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.

In the photographic material of the present invention, an image stabilizer and an ultraviolet absorber can be used 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, generally known color photographic processing can be performed after exposure.

[0081]

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 in which polyethylene was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, each layer having the composition shown in Tables 1 and 2 below was coated with titanium oxide. The sample was applied on the side of the polyethylene layer to be prepared, whereby a multilayer color photographic material sample 101 was prepared.

[0083]

[Table 1]

[0084]

[Table 2]

The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (EY-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (S
T-2) 6.67 g, stain inhibitor (HQ-1) 0.
60 cc 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 the following blue-sensitive silver halide emulsion (containing 8.67 g of silver), and an anti-irradiation dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. (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 each of the above-mentioned layers are shown below.

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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The silver halide emulsions used for the first, third and fifth layers are as follows. The chemical sensitizer, stabilizer and sensitizing dye used in each emulsion are also shown below.

Blue-sensitive silver halide emulsion (Em-B) Monodispersed cubic silver chlorobromide emulsion having an average particle 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-14 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-21 × 10 ^-4 mol / mol AgX Green-sensitive silver halide emulsion (Em-G) Monodispersed cubic silver chlorobromide having an average particle size of 0.43 μm, a coefficient of variation = 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 sensitivity 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

[0097]

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Next, the magenta coupler EM-1 in the third layer of the sample 101 was replaced with the magenta coupler of the present invention shown in Table 3 in the same amount as the amount added of the magenta coupler EM-1 as shown in Table 3 below. Is sample 1 in the same manner as sample 101.
Nos. 02 to 109 were produced.

Each of the samples thus produced was subjected to wedge exposure with green light according to 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 each processing solution 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 Replenisher 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 Fluorescent brightener (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g 1 8.8 g Potassium carbonate 27 g 27 g Water was added to make the total volume 1000 cc. The pH of the tank solution was 10.10, and the pH of the replenisher was 10.
Adjust to 60.

Bleaching / fixing solution (tank solution and replenisher are the same) Ferric ammonium diaminetetraacetate 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 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 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 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 10 days, and the residual ratio (%) of the dye image at an initial density of 1.0 was determined.

Table 3 shows the results.

[0108]

[Table 3]

As is evident from Table 3, Samples 102 to 109 using the magenta coupler of the present invention are superior in both color development and light resistance as compared with Sample 101 using the comparative magenta coupler. .

[0110]

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

Continuing from the front page (72) Inventor Shuichi Sugita 1 Konica Corporation, Sakuracho, Hino-shi, 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 (M-1). Embedded image [In the formula, R ₁ represents a substituent, and R ₂ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. X ₁ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. Z ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. Z ₂ represents a nonmetallic atom group necessary for forming a cyclic hydrocarbon or a heterocyclic ring, and X ₂ represents> CＣO or> S (＝ O) ₂ . ]