JPH10142757A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material contg. a magenta coupler excellent in color forming property and forming a magenta dye image having remarkably improve light fastness by incorporating a specified magenta coupler into one of green-sensitive silver halide emulsion layers. SOLUTION: At least one kind of magenta coupler represented by the formula is incorporated into at least one of green-sensitive silver halide emulsion layers. In the formula, R1 is a substituent, R2 is acyl, sulfonyl, etc., each of R3 and R4 is H or alkyl, each of R5 and R6 is H, alkyl, etc., L1 is alkylene or arylene, L2 is *-OCO-, *-N(R7 )CO- or -SO2 -(* shows the direction of bonding to the pyrazolotriazole ring), R7 is H or alkyl, L3 is alkylene, L4 is alkylene or arylele, each of (m) and (n) is 0 or 1 and X is H or a group releasable by reaction with the oxidized body of a color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), couplers generally used include yellow couplers comprising open-chain ketomethylene compounds, pyrazolone compounds and pyrazoloazole compounds. Magenta couplers, cyan couplers composed of phenolic compounds and naphthol compounds are known.

Heretofore, 5-pyrazolone compounds have been frequently used as magenta couplers. Known pyrazolone magenta couplers include U.S. Pat.
Nos. 88 and 3,519,429, JP-A-49-111
No. 631, No. 57-35858 and the like.

[0004] However, the Theory of the Photographic Process (The Theory of the Photographic Process)
the Photographic Procedures
s), Macmillan, 4th edition (1977), 356-35
8 pages, Fine Chemicals, CMC, 14
Vol. 8, No. 38, pp. 38-41, Dyes formed from pyrazolone magenta couplers have undesirable side absorption as described in the Abstracts of the Photographic Society of Japan, Annual Meeting of 1985, pp. 108-110. There is a need for improvements.

As described in the above literature, the dye formed from the pyrazoloazole type magenta coupler has no side absorption. The fact that this coupler is a good coupler is described in the above-mentioned documents in U.S. Pat. Nos. 3,725,067, 3,758,309 and 3,810,761.

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

[0007] 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.

[0010]

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 coupler having excellent coloring properties and a magenta dye image having remarkably improved light fastness. To provide a silver halide color photographic light-sensitive material.

[0011]

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

On a support, a blue-sensitive silver halide emulsion layer,
In a silver halide color photographic light-sensitive material having a photographic component layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, at least one of the green-sensitive silver halide emulsion layers has the following general formula (M- A silver halide color photographic light-sensitive material comprising at least one magenta coupler represented by 1).

[0013]

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In the formula, R ₁ represents a substituent, and R ₂ represents an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group and a sulfamoyl group. R ₃ and R ₄ each represents a hydrogen atom or an alkyl group, when R ₃ and R ₄ represents an alkyl group, R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a -CH ₂ OR _6, R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an acyl group. L ₁ represents an alkylene group or an arylene group, L ₂
The * -OCO -, * - N ( R 7) CO- or -SO ₂ -
(* Represents the bonding direction with the pyrazolotriazole nucleus). R ₇ represents a hydrogen atom or an alkyl group. L ₃ represents an alkylene group, and L ₄ represents an alkylene group or an arylene group. m and n each represent 0 or 1, and when m = 0, n = 0. In addition, L ₂ is * -N
When (R ₇ ) CO— represents m = 1, L ₂ represents —SO ₂
When expressing-, m = n = 0. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

Hereinafter, the present invention will be described 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 ₁ may be an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group). Group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group, A naphthyl group), a heterocyclic group (eg, a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a piperidinyl group, a pyrazolyl group, Tetrazolyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, iodine Child, such as a fluorine atom), an alkoxy group (e.g., methoxy group, ethoxy group, propyloxy group, a pentyloxy group, cyclopentyloxy group,
Hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc., aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyl) Oxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group) Butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino, octylsulfonylamino, dodecylsulfonylamino, phenylsulfonylamino, etc.), Famoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl Aminosulfonyl group, 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.), acyl group (eg, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbony) Group, octyl group, 2-ethylhexyl group,
Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl Group, 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, Sill carbonylamino group, an octyl carbonylamino group, a dodecyl carbonylamino 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, etc., and these groups may be further substituted by the above substituents. .

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 an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group.

Examples of the acyl group represented by R ₂ include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, a pentylcarbonyl group, a cyclohexylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a dodecylcarbonyl group and a phenylcarbonyl group. , A naphthylcarbonyl group, a pyridylcarbonyl group and the like.

The sulfonyl group represented by R _{2 includes} , for example, methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, phenylsulfonyl, naphthylsulfonyl, 2- And a pyridylsulfonyl group.

Examples of the alkoxycarbonyl group represented by R ₂ include a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

The aryloxycarbonyl group represented by R _{2 includes} , for example, a phenyloxycarbonyl group and a naphthyloxycarbonyl group.

Examples of the carbamoyl group represented by R ₂ include an aminocarbonyl group, a methylaminocarbonyl group,
Dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-
Examples include an ethylhexylaminocarbonyl group, a dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, and a 2-pyridylaminocarbonyl group.

Examples of the sulfamoyl group represented by R ₂ include aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylamino Examples include a sulfonyl group, a phenylaminosulfonyl group, a naphthylaminosulfonyl group, a 2-pyridylaminosulfonyl group, and the like.

An acyl group, a sulfonyl group represented by R ₂ ,
The alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, or the sulfamoyl group may have a substituent, and examples of the substituent include the same groups as R ₁ in formula (M-1).

Preferred as R ₂ is an acyl group or a sulfonyl group.

In the general formula (M-1), R ₃ and R ₄ each represent a hydrogen atom or an alkyl group.

Examples of the alkyl group represented by R ₃ and R ₄ include, for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl And the like.

When R ₃ and R ₄ both represent an alkyl group, R ₃ and R ₄ may combine with each other to form a ring.

The alkyl group represented by R ₃ and R ₄ may have a substituent, and examples of the substituent include the same groups as R ₁ in formula (M-1).

Preferred for R ₃ and R ₄ is a hydrogen atom.

In the general formula (M-1), R ₅ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or —CH ₂ OR ₆ .

The alkyl group represented by R ₅ has the same meaning as the alkyl group represented by R ₃ and R ₄ in formula (M-1).

The alkenyl group represented by R _{5 includes} , for example, an allyl group.

As the aryl group represented by R ₅ , for example,
Examples include a phenyl group and a naphthyl group.

The alkyl group, alkenyl group or aryl group represented by R ₅ may have a substituent, and examples of the substituent include groups similar to R ₁ in formula (M-1). .

Preferred for R ₅ is —CH ₂ OR ₆
It is.

In the general formula (M-1), R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an acyl group.

The alkyl group represented by R ₆ has the same meaning as the alkyl group represented by R ₃ and R ₄ in formula (M-1).

The alkenyl group represented by R ₆ has the same meaning as the alkenyl group represented by R ₅ in formula (M-1).

The aryl group represented by R ₆ has the same meaning as the aryl group represented by R ₅ in formula (M-1).

The acyl group represented by R ₆ has the same meaning as the acyl group represented by R ₂ in formula (M-1).

The alkyl group, alkenyl group, aryl group or acyl group represented by R ₆ may have a substituent, and examples of the substituent include the same groups as R ₁ in formula (M-1). be able to.

In the formula (M-1), L ₁ represents an alkylene group or an arylene group.

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

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

The alkylene group or arylene group represented by L ₁ may have a substituent, and examples of the substituent include the same groups as R ₁ in formula (M-1).

[0049] are shown below, but typical examples of the alkylene group or an arylene group represented by L _1, L ₁ is not limited thereto.

[0050]

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Preferred for L ₁ is an alkylene group.

In the general formula (M-1), L ₂ represents *
Represents —OCO—, * —N (R ₇ ) CO— or —SO ₂ — (* represents the bonding direction with the pyrazolotriazole mother nucleus).

R ₇ represents a hydrogen atom or an alkyl group.

As the alkyl group represented by R ₇ , for example,
Methyl group, ethyl group, propyl group, isopropyl group, t
tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group and the like.

When R ₇ represents an alkyl group, it may have a substituent, and examples of the substituent include the same groups as R ₁ in formula (M-1).

Preferred for R ₇ is a hydrogen atom.

Preferred for L ₂ is * -OCO-
Or * -N (R ₇₎ is a CO-.

In the formula (M-1), L ₃ represents an alkylene group.

The alkylene group represented by L ₃ has the same meaning as the alkylene group represented by L ₁ in formula (M-1).

In the formula (M-1), L ₄ represents an alkylene group or an arylene group.

The alkylene group or arylene group represented by L ₄ is the same as the alkylene group or arylene group represented by L ₁ in formula (M-1).

In the general formula (M-1), m and n each represent 0 or 1, and when m = 0, n = 0.
It is. Further, an m = 1 when L ₂ is * -N represents a (R ₇₎ CO-, L ₂ is -SO ₂ - is m = n = 0 to represent a.

In the general formula (M-1), an atom which can be eliminated by a reaction with an oxidized form of the color developing agent represented by X,
Examples of the group include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, and the like) and alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio,
Examples include alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, preferably a halogen atom, particularly a chlorine atom. is there.

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.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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

A typical synthesis example of the magenta coupler represented by formula (M-1) of the present invention is shown below.

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

[0075]

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4.67 g of the compound [A] was dissolved in 47 ml of acetonitrile and heated under reflux. The compound [B]
A solution prepared by dissolving 1.07 g in 5 ml of acetonitrile was added to 2
It was added dropwise over 0 minutes. After heating and refluxing for 1 hour after the completion of the dropwise addition, the mixture was allowed to cool. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane) to obtain 3.00 g of compound [C].

3.00 g of the compound [C] obtained above was dissolved in 30 ml of ethyl acetate, and a solution of 2.89 g of anhydrous sodium acetate dissolved in 30 ml of water was added thereto. Further, a solution obtained by dissolving 2.38 g of the compound [D] in 10 ml of ethyl acetate was slowly dropped with vigorous stirring.
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. The 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 obtain 4.25 g of oily exemplary compound (1-1). .

The identification was performed by MASS and NMR spectra, and it was confirmed that it was Exemplified Compound 1-1.

Synthesis Example 2 << Synthesis of Exemplified Compound 1-50 >>

[0080]

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3.90 g of the compound [E] was dissolved in 39 ml of acetonitrile, and the mixture was heated under reflux. The compound [F]
A solution obtained by dissolving 1.50 g in 7 ml of acetonitrile was added to 2
It was added dropwise over 0 minutes. After heating and refluxing for 1 hour after the completion of the dropwise addition, the mixture was allowed to cool. The reaction solution was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (silica gel, developing solvent: ethyl acetate / n-hexane) to obtain 3.51 g of compound [G].

3.50 g of the compound [G] obtained above was dissolved in 35 ml of ethyl acetate, and a solution of 2.66 g of anhydrous sodium acetate dissolved in 30 ml of water was added thereto. Furthermore, a solution in which 2.01 g of the compound [H] was dissolved in 10 ml of ethyl acetate was slowly dropped with vigorous stirring.
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. The 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 obtain 4.59 g of oily exemplary compound (1-50). .

The identification was performed by MASS and NMR spectra, and it was confirmed that it was Exemplified Compound 1-50.

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

[0085]

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In the general formula [A], R ₂₁ is a hydrogen atom,
Represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and among these, as the alkyl group, for example, methyl,
Examples thereof include linear or branched alkyl groups such as ethyl, propyl, octyl, t-octyl, benzyl, and hexadecyl groups. The alkenyl group represented by R ₂₁ includes, for example, allyl, hexenyl, octenyl and the like. Examples of the aryl group for R ₂₁ include phenyl and naphthyl groups. Further, specific 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.

Each of R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ represents 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. Groups and aryl groups are the alkyl groups described for R ₂₁ above,
The same as the alkenyl group and the aryl group can be mentioned.

As the halogen atom, for example, fluorine,
Each atom such as chlorine and bromine can be mentioned. Further, specific examples of the alkoxy group include methoxy, ethoxy, and benzyloxy.

The acylamino group is represented by R ₂₇ CONH—, wherein R ₂₇ is an alkyl group (for example, methyl, ethyl, propyl, butyl, octyl, t-octyl, benzyl, etc.), an alkenyl group (for example, allyl, octenyl, It can represent an aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (eg, pyridinyl, pyrimidyl).

R ₂₄ represents 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 closed with each other to form a 5- to 6-membered heterocyclic ring, and R ₂₃ and R ₂₄ may be closed with each other to form a 5-membered ring. These rings include those in which another ring is spiro-bonded.

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

[0093]

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[0094]

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[0095]

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[0096]

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

[0098]

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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, an alkenyl group. Represents a group, a cycloalkyl group or an aryl group, and r represents an integer of 0 to 3.
When two or more R ₃₁ and R ₃₂ are present in the compound,
Each of R ₃₁ and R ₃₂ may be the same or different. Y ₁ is-
S -, - SO -, - represents a or an alkylene group - SO _2.

As the secondary or tertiary alkyl group or the secondary or tertiary alkenyl group represented by R ₃₁ ,
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,
Each group such as i-propenyl and 2-hexenyl is exemplified.

The alkyl group represented by R32 is preferably one having 1 to ₃₂ carbon atoms, and the alkenyl group is preferably one having 2 to ₃₂ carbon atoms, and may be linear or branched.

Specifically, methyl, ethyl, t-butyl,
Examples include groups such as pentadecyl, 1-hexylnonyl, 2-chlorobutyl, benzyl, 2,4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl, and isopropenyl.

The cycloalkyl groups represented by R ₃₁ and R ₃₂ are preferably those having 3 to 12 carbon atoms, and include 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, 2,4-di-t-phenyl -Amylphenyl, 3-hexadecyloxyphenyl, α-naphthyl and the like.

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

Each of the groups represented by R ₃₁ , R ₃₂ and Y ₁ may have a substituent. Examples of the substituent include a halogen atom and nitro, cyano, amide, sulfonamide and alkoxy. , Aryloxy, alkylthio, arylthio, acyl and the like.

The typical examples of the general formula [B] are shown below, but the present invention is not limited to these.

[0108]

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[0109]

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[0110]

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

The amount of the image stabilizer represented by the general formula [A] or the general formula [B] is determined in accordance with the general formula (M-
For the magenta coupler shown in 1), 5
It is preferably from 400 to 400 mol%, more preferably from 10 to 250 mol%.

The magenta coupler represented by formula (M-1) of the present invention and the above-mentioned image stabilizer are preferably used in the same layer. 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, a method using a known 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 mixed solution of a low-boiling solvent 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 of the present invention represented by 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, 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, 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.

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 a 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.

[0126]

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

[0128]

[Table 1]

[0129]

[Table 2]

A 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 g of ethyl acetate was added to and dissolved in 67 g of 6.67 g of a high boiling point organic solvent (DNP), and the solution was dissolved in 220 cc of a 10% aqueous gelatin solution containing 7 cc of a 20% aqueous surfactant (SU-2) solution using an ultrasonic homogenizer. This was emulsified and dispersed to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (AIY-1) was further added 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. (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.

[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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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-2 1 × 10 ⁻⁴ mol / mol AgX green-sensitive silver halide emulsion (Em-G) Monodisperse cubic 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% Silver emulsion Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX Red-sensitive silver halide emulsion (Em R) Monodisperse cubic silver chlorobromide emulsion having an average particle size of 0.50 µm, a coefficient of variation of 0.08, and a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / Molar AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX

[0142]

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Next, the magenta coupler EM-1 in the third layer of the sample 101 was replaced with a magenta coupler of the present invention or a comparative magenta coupler shown in the following Table 3 having an equimolar amount to the addition amount of the magenta coupler EM-1. Samples 102 to 118 were produced in the same manner as Sample 101 except that the image stabilizer was changed as shown in Table 3. Note that the structural formula of the magenta coupler EM-2 used for the comparative sample is EM described above.
It is shown together with -1.

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 2.8 g Potassium carbonate 27 g 27 g Water was added to make the total amount 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 ammonium diaminetetraacetate 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.

[0153]

[Table 3]

As is clear from Table 3, samples 101 to 1
In Sample No. 18, Samples 105 to 114 using the magenta coupler of the present invention showed a very large improvement in light resistance as compared with Samples 102 and 104 using the comparative magenta coupler.

Further, it was found that the effects of the samples 115 to 118 in which the dye image stabilizer was used in combination with the magenta coupler of the present invention were further amplified.

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

[0157]

As demonstrated in the examples, the silver halide color photographic light-sensitive material of the present invention is excellent in the color developing properties of magenta couplers and the light fastness of magenta dye images is remarkably improved and has an excellent effect.

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 an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group. R ₃ and R ₄ each represents a hydrogen atom or an alkyl group, when R ₃ and R ₄ represents an alkyl group, R ₃
And R ₄ may combine with each other to form a ring. R ₅ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or -
Represents CH ₂ OR ₆ , wherein R ₆ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an acyl group. L ₁ represents an alkylene group or an arylene group, and L ₂ represents * —OC
O—, * —N (R ₇ ) CO— or —SO ₂ — (*
Represents the bonding direction with the pyrazolotriazole mother nucleus). R
₇ represents a hydrogen atom or an alkyl group. L ₃ represents an alkylene group, and L ₄ represents an alkylene group or an arylene group. m and n each represent 0 or 1;
When n, n = 0. Further, L ₂ is * -N (R ₇ ) CO
- a m = 1 to represent a, L ₂ is -SO ₂ - is m = n = 0 to represent a. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ]