JPH095959A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain an excellent color developing property and to improve the lightfastness of a magenta pigment picture by incorporating at least one kind of specified coupler into the green-sensitive silver halide emulsion layer. CONSTITUTION: At least one kind of coupler expressed by the formula is incorporated into at least one green-sensitive silver halide emulsion layer. In the formula, R is hydrogen atom or a substituent, R1 to R4 are hydrogen atom or an alkyl, R5 is a group capable of being substituted into a benzene ring, Y1 is oxygen atom or NR6 (R6 is hydrogen atom or an alkyl), Y2 is an alkylene group, oxygen atom, sulfur atom or sulfonyl group, X1 is hydrogen atom or a group capable of being released by the reaction with the oxidant of a color developing agent, Z is a nonmetallic atom group to form a nitrogen-contg. heterocyclic ring, n1 is an integer of 0 to 3, and n2 is an integer of 0 to 4. Meanwhile, although the magenta coupler and picture stabilizer are preferably used in the layer, the stabilizer may be used in the layer adiacent to the layer wherein the coupler is present.

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 specifically, by containing a novel pyrazolotriazole-based magenta coupler, it has excellent color reproducibility and color developability. Further, it relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image which is stable to heat and light.

[0002]

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

Heretofore, 5-pyrazolone compounds have been often used as magenta couplers. Known pyrazolone magenta couplers include U.S. Pat.
3,519,429, JP-A-49-111631, JP-A-57-35858 and the like. But the Theory of the Photog
raphic Process), Macmillan, 4th edition (1977), 356
~ 358 pages, Fine Chemicals, published by MC MC, 1
As described in Volume 4, No. 8, pp. 38-41, Proceedings of Annual Meeting of the Photographic Society of Japan, 1985, pp. 108-110, dyes formed from pyrazolone magenta couplers have undesirable side absorption. Yes, and its improvement is desired.

As described in the above-mentioned literature, the dye formed from the pyrazoloazole type magenta coupler has no side absorption. That this coupler is a good coupler, U.S. Pat.
No. 3,810,761 etc.

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 Nos. 59-125732 and 6
1-282845, 61-292639, and 61-279855 disclose a technique of using a pyrazoloazole-based magenta coupler in combination with a phenol compound or a phenyl ether compound.
61-72246, 62-208048, 62-157031, 63-163
No. 351 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 objects of the present invention have been attained by the following constitutions.

(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 represents a hydrogen atom or a substituent. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group. R ₅ represents a group capable of substituting on the benzene ring.
Y ₁ represents an oxygen atom or NR ₆ , and R ₆ represents a hydrogen atom or an alkyl group. Y ₂ is an alkylene group, an oxygen atom,
Represents a sulfur atom or a sulfonyl group. X ₁ represents a hydrogen atom or a group capable of leaving by a reaction with an oxidized product of a color developing agent. Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 4. (2). 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-2).

[0014]

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[In the formula, R ₁₀ represents a hydrogen atom or a substituent. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or an alkyl group. Y ₁₁ represents an oxygen atom or NR ₁₅ , and R ₁₅ represents a hydrogen atom or an alkyl group. L represents an arylene group. Z'represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. X ₁₁ represents a hydrogen atom or a group capable of leaving by a reaction with an oxidized product of a color developing agent.
n ₁₁ represents an integer of 0 to 3. Hereinafter, the present invention will be described in detail.

The magenta coupler represented by the general formula (M-1) and the general formula (M-2) of the present invention will be described.

The general formula (M-1) and the general formula (M-
In 2), the substituent represented by R and R ₁₀ is an alkyl group (for example, a methyl group, an ethyl group, a propyl group,
Isopropyl group, tert-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.) , An aryl group (eg, phenyl group, naphthyl group, etc.), a 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 (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group) , A pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, an octyloxy group, a dodecyloxy group, and the like, an aryloxy group (for example, a phenoxy group, a naphthyloxy group, and the like), an alkoxycarbonyl group (for example, methyloxy Carbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.) A sulfonamido group (e.g.,
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, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group Group, etc.), ureido group (eg, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, Chiruureido group, dodecyl ureido group, a phenyl ureido group, Nafuchiruureido 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, dimethylaminocarbonyl group, propyl) Aminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, octylaminocarbonyl group Dodecylaminocarbonyl 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. It may be substituted by the substituent of. Of these,
For example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio,
Arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoyl Each group such as amino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and carboxyl is preferable, more preferable is an alkyl group,
Particularly preferred is a t-butyl group.

R ₁ and R ₂ are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, cyclopentyl group,
Hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.) are preferable, and these groups may be further substituted with a substituent represented by R and R ₁₀ .

R ₁₁ and R ₁₂ are alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, cyclopentyl group,
Hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.) are preferable, and these groups may be further substituted with a substituent represented by R and R ₁₀ .

Examples of the group capable of substituting on the benzene ring represented by R ₅ include the same groups as the substituents represented by R and R _10. Of these, for example, alkyl, cycloalkyl, alkenyl , Aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom,
Heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino Preferable examples thereof include aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and carboxyl groups.

The group represented by Y ₂ is preferably an alkylene group (eg methylene group, ethylene group, propylene group, —CH ₂ OCH ₂ —, isopropylene group, tert-group).
Butylene group, pentylene group, cyclopentylene group, hexylene group, cyclohexylene group, octylene group, dodecylene group, etc.), sulfonyl group and the like, more preferably,
It is a sulfonyl group. The alkylene group may further have a substituent, and the substituent is the same as in the case of R ₅ ,
Further, an alkylene group (eg, butylene group, pentylene group, hexylene group, etc.) and the like can be mentioned.

Examples of the arylene group represented by L include groups such as phenylene group and naphthalene group. These groups may further have a substituent, and the substituent is R
The same groups as ₅ can be mentioned.

R, R ₁₀ , R ₁ , R ₂ , R ₁₁ , R ₁₂ , R
_The groups represented by ₅ , Y ₂ and L may be further substituted with the substituents represented by R and R ₁₀ .

N ₁ is preferably 1.

N ₁₁ is preferably 1.

Examples of the group represented by X ₁ and X _{11 which} can be eliminated by the reaction with the oxidation product of the color developing agent include, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, and heterocycle. Oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy,
Aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio,
Arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,
And the like, and preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or 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 couplers represented by formulas (M-1) and (M-2) of the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

[Chemical 12]

[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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The magenta couplers represented by the above general formulas (M-1) and (M-2) of the present invention are the Journal of the Chemical Society (Journal of the Chemical Society).
Chemical Society), Perkin I (1977), 2
047-2052, U.S. Pat.No. 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 60-3
No. 3552, No. 60-43659, No. 60-172982, No. 60-190779
No. 61-189539, No. 61-241754, No. 63-163351,
62-157031, Synthesys, 1981, p. 40, 1984, 122.
Pp. 894, 894, JP-A-49-53574, British Patent 1,41
0,846, New Experimental Chemistry Course 14-III, pp. 1585-1594 (197
7), published by Maruzen, Helv. Chem. Acta., 36, 75 (1953),
J. Am. Chem. Soc., 72, 2762 (1950), Org. Synt
h., Volume II, page 395 (1943), etc., can be easily synthesized by those skilled in the art.

Next, typical synthetic examples of the magenta couplers represented by the general formula (M-1) and the general formula (M-2) of the present invention are shown below.

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

[0045]

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Compound (I) described in Japanese Patent Application No. 5-320185 5.
9 g was dissolved in 50 ml of toluene, and further 7.0 g of compound (II),
4.6 g of tosyl acid monohydrate was added, and the mixture was refluxed for 16 hours while removing water purified by the reaction. After cooling to room temperature, 150 ml of toluene was further added to wash with water. After separating the toluene layer, toluene was removed by vacuum distillation. The obtained fraction was purified by column chromatography (developing solvent: ethyl acetate, hexane) to obtain 2.6 g of the desired product (Exemplified Compound 1-1). (Yield 24%, colorless oil) Identification was performed by MASS, NMR, and IR spectra, and it was confirmed that the compound was Exemplified Compound 1-1.

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

[0048]

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Compound (I) described in Japanese Patent Application No. 5-320185 9.
8 g was dissolved in 50 ml of toluene, and 6.9 g of compound (II),
6.0 g of tosyl acid monohydrate was added, and the mixture was refluxed for 16 hours while removing water purified by the reaction. After cooling to room temperature, 120 ml of toluene was further added to wash with water. After separating the toluene layer, toluene was removed by vacuum distillation. The obtained fraction was purified by column chromatography (developing solvent: ethyl acetate, hexane) to obtain 3.9 g of the desired product (Exemplified compound 2-2). (Yield 26%, colorless oil) Identification was performed by MASS, NMR, and IR spectra, and it was confirmed that the compound was Exemplified Compound 2-1.

The general formula (M-1) and the general formula (M
-2) is a magenta coupler represented by the following general formula [A] and / or general formula [B], which is also referred to as the magenta coupler of the present invention or the coupler of the present invention. It can be used in combination with the agent.

[0051]

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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,
Ethyl, propyl, octyl, t-octyl, benzyl,
A straight chain or branched alkyl group such as a hexadecyl group may be mentioned. 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,
Specific examples include methoxy, ethoxy, and benzyloxy groups. The acylamino group is represented by R ₂₇ CONH-, and R ₂₇ is an alkyl group (eg, methyl, ethyl, propyl, butyl, octyl, t-octyl, benzyl, etc.), an alkenyl group (eg, allyl, octenyl, oleyl, etc.). Each group), an aryl group (for example, each group of phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (for example, each group of 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.

[0057]

[Chemical 21]

[0058]

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[0059]

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[0060]

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The compound represented by the general formula [A] is a compound of the Journal of the Chemical Society.
the Chemical Society), pp. 415-417 (1962), 2904-
2914 (1965); The Journal of Organic Chemistr
y), 23, 75-76; Tetrahedron 26.
Volume, 4743-4751 (1970); Chemical Letter (Chem., Le
tt.), (4), pp.315-316 (1972); Journal of the Chemical Society of Japan, No.1
0, 1987-1990 (1972); Bulletin of Chemical Society of Japan, 53, 555-556 (1980) and the like.

[0062]

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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 n ² 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.

The secondary or tertiary alkyl group represented by R ₃₁ or the secondary or tertiary alkenyl group is
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, i-propenyl, Examples include groups such as 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, methyl, ethyl, t-butyl, pentadecyl,
1-hexylnonyl, 2-chlorobutyl, benzyl, 2,4-di
-t-amylphenoxymethyl, 1-ethoxytridecyl,
Examples include groups such as allyl and isopropenyl.

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

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 or 2,4-diphenyl group.
-t-amylphenyl, 3-hexadecyloxyphenyl,
Examples include α-naphthyl and the like.

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

Each of these 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, amide, sulfonamide, alkoxy and aryloxy. And groups such as alkylthio, arylthio, and acyl.

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

[0071]

[Chemical formula 26]

[0072]

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[0073]

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The compound represented by the general formula [B] is represented by US Pat. No. 2,807,653, Journal of the Chemical Society Perkin I (J. Chem. Soc. Perkin I) 1.
It can be synthesized according to the method described on page 712 (1979).

The amount of the image stabilizer represented by the general formula [A] or the general formula [B] is preferably 5 to 400 mol% with respect to the magenta coupler of the present invention. It is preferably 10 to 250 mol%.

The magenta coupler of the present invention and the image stabilizer are preferably used in the same layer, but the image stabilizer may be used in a layer adjacent to the layer in which the coupler is present.

The magenta coupler of the present invention is usually 1 × 10 ^-3 mol to 8 × 10 ^-1 mol, preferably 1
It can be used in the range of × 10 ^-2 mol to 8 × 10 ^-1 mol.

The magenta coupler of the present invention can be used in combination with other types of magenta couplers.

In order to incorporate the magenta coupler of the present invention, a conventional method, for example, a mixture of a known high-boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low-boiling solvent such as butyl acetate and ethyl acetate is used. Alternatively, after dissolving the magenta coupler of the present invention alone or in combination in a solvent having only a low boiling point solvent,
A method of mixing with a gelatin aqueous solution containing a surfactant, emulsifying and dispersing using a high-speed rotating mixer, a colloid mill or an ultrasonic dispersing machine, and then directly adding the resulting emulsion 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 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, but both compounds are simultaneously dissolved, dispersed and added to the emulsion. The method is preferred.

The amount of the high boiling point solvent added is preferably 0.01 to 10 g, more preferably 0.1 to 3.0 g, based on 1 g of the magenta coupler of the present invention.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions 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 oxidant of a developing agent, which have an effect of color correction, are subjected to a coupling reaction. Compounds that release photographically useful fragments such as hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

Further, in the light-sensitive material of the present invention, an image stabilizer and an ultraviolet absorber can be used for the purpose of preventing 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.

[0089]

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 polyethylene 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. A multilayer color photographic light-sensitive material sample 101 was prepared by coating on the side of the contained polyethylene layer.

[0091]

[Table 1]

[0092]

[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 (ST-2)
To 6.67 g, stain inhibitor (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g, 60 cc of ethyl acetate was added and dissolved, and this solution was dissolved in 20% surfactant (SU-2) aqueous solution 7
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 cc of 10% gelatin aqueous solution containing cc using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation 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.

[0098]

[Chemical 29]

[0099]

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[0100]

[Chemical 31]

[0101]

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[0102]

[Chemical 33]

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

Blue-sensitive silver halide emulsion (Em-B) Average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide emulsion 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-14 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX green-sensitive silver halide emulsion (Em-G) average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide 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-14 4 × 10 ^-4 mol / mol AgX Red-sensitive silver halide emulsion (Em-R) Average grain size 0.50 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic silver chlorobromide emulsion 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-11 1 × 10 ^-4 mol / mol AgX

[0105]

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Next, the coupler EM- of the third layer of Sample 101 was used.
Sample 101 except that 1 was replaced with a coupler of the present invention shown in Table 3 below or a comparative coupler in which the amount of the coupler EM-1 was 1/2 mol, and the dye image stabilizer was changed as shown in Table 3. Samples 102 to 136 were manufactured in the same manner as in. 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.

Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Composition of each processing solution is as follows. Show. The replenishing amount of each processing solution is 80 cc / m ^{2 of} color photographic light-sensitive material.

Color developer tank solution Replenishing solution Pure water 800cc 800cc Triethanolamine 10g 18g N, N-diethylhydroxylamine 5g 9g Potassium chloride 2.4g-1-hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N- Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water The total volume is adjusted to 1000 cc by adjusting pH 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 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100cc Ammonium sulfite (40% aqueous solution) 27.5cc Add water Adjust the total volume to 1000cc and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher 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 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenedisulphonic acid derivative) 1.5 g Water is added to bring the total amount to 1000 cc, and pH is 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

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 12 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.

[0116]

[Table 3]

As is clear from Table 3, in Samples 101 to 128, Samples 105 to 128 using the coupler of the present invention have much higher light resistance than Samples 102 and 104 using the comparative coupler. The improvement was observed, and further, compared with Comparative Samples 101 and 103 in which two kinds of dye image stabilizers were used in the comparative coupler, the above-mentioned Samples 105 to 128 of the present invention did not contain the dye image stabilizer. Nevertheless, a significant improvement in light resistance was observed.

Further, it was found that in Samples 129 to 136 in which the dye image stabilizer was used in combination with the coupler of the present invention, the effect was further amplified.

It was also confirmed that the coupler of the present invention has the same or higher color-developing property as compared with the comparative coupler, even though the amount added is reduced by half.

[0120]

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

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hiroyuki Yasukawa 1st Sakura-cho, Hino City, Tokyo Konica Stock Company In-house

Claims (2)

[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 represents a hydrogen atom or a substituent. R ₁ ,
R ₂ , R ₃ and R ₄ represent a hydrogen atom or an alkyl group. R ₅ represents a group capable of substituting on the benzene ring. Y ₁ represents an oxygen atom or NR ₆ , and R ₆ represents a hydrogen atom or an alkyl group. Y ₂ represents an alkylene group, an oxygen atom, a sulfur atom or a sulfonyl group. X ₁ represents a hydrogen atom or a group capable of leaving by a reaction with an oxidized product of a color developing agent. Z
Represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring. n ₁ represents an integer of 0 to 3, and n ₂ represents an integer of 0 to 4. ] 2. 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 coupler represented by the following formula (M-2). Embedded image [In the formula, R ₁₀ represents a hydrogen atom or a substituent. R ₁₁ ,
R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or an alkyl group. Y ₁₁ represents an oxygen atom or NR ₁₅ , and R ₁₅ represents a hydrogen atom or an alkyl group. L represents an arylene group. Z'represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle. X ₁₁ represents a hydrogen atom or a group capable of leaving by a reaction with an oxidized product of a color developing agent. n ₁₁ is 0 to 3
Represents the integer. ]