JPH05241289A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and color developing performance and to improve the lightfastness of a magenta dye image by incorporating a specified magenta coupler. CONSTITUTION:This color photographic sensitive material contains at least one magenta coupler represented by formula I in which A is the residue obtained by removing R2 or R3 from a pyrazolotriazole magenta coupler represented by formula II or the like; L is a divalent bonding group or a simple bond; Z is-O-,-S-, or -N(Ra)-; each of Ra, R1, and R2 is H or a substituent; each of R11 and R12 is independent from each other and may condense with each other to form a 5, 6, or 7-membered ring; and X is a group to be released by coupling with the oxidation product of a color developing agent. This coupler may be used together with another kind of magenta coupler.

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 pyrazoloazole-based magenta coupler, excellent color reproducibility and color developability, Furthermore,
The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image which is stable against heat and light.

[0002]

BACKGROUND OF THE INVENTION In silver halide color photographic light-sensitive materials, couplers generally used include yellow couplers composed of open-chain ketomethylene compounds, pyrazolone compounds, magenta couplers composed of 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 3,519,429, and JP-A-49-1.
11631, 57-35858, etc. But,
The Theory of the Photographic Process, Macmillan, 4th edition (1977), pages 356-358, Fine Chemicals, CMC, Vol. 14, No. 8 , Pp. 38-41, Proceedings of the Annual Meeting of the Photographic Society of Japan, 1985, 108-110
As described on the page, the dye formed from the pyrazolone magenta coupler has unfavorable side absorption, and its improvement is desired.

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

However, the fastness to light of the azomethine dyes formed from these couplers is extremely low, and the performance of color photographic light-sensitive materials, especially print color photographic light-sensitive materials, is markedly impaired.

[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 the magenta dye image is insufficient, and its improvement has been strongly desired.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in color reproducibility and color developability and in which the light fastness of a magenta dye image is remarkably improved.

[0010]

The above object of the present invention is to provide a compound represented by the following general formula [I]
And a silver halide color photographic light-sensitive material characterized by containing at least one magenta coupler represented by

[0011]

[Chemical 3]

[Wherein A is the following general formula [II] or [II]
I] represents a residue obtained by removing R ₁ or R ₂ from a pyrazolotriazole magenta coupler represented by I, L represents a divalent linking group or a simple bond, and -O-, -S- or -N ( R
a)-, Ra represents a hydrogen atom or a substituent, R ₁₁
And R ₁₂ represent a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be the same or different, and may be condensed with each other to form a 5- to 7-membered ring. ]

[0013]

[Chemical 4]

[In the formula, R ₁ and R ₂ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. The present invention will be described more specifically below.

In the above general formulas [I], [II] and [III], the substituents represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra are not particularly limited, but they are typically Examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and other groups. In addition to these, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl , Carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryl Oxy Each group such as carbonyl and heterocyclic thio,
Also, a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned.

The alkyl group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra is preferably a phenyl group.

Examples of the acylamino group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra include an alkylsulfonylamino group and an arylsulfonylamino group.

Alkylthio groups represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra, the alkyl component in the arylthio group, and the aryl component are the above R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra.
And an alkyl group and an aryl group represented by.

The alkenyl group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra has _{2 to} 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms. The alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra has 3 to 12 carbon atoms, especially 5 to 5 carbon atoms.
7 is preferable.

The sulfonyl group represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ and Ra is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like; a phosphonyl group. Examples include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; Groups etc .; as sulfamoyl groups, alkylsulfamoyl groups, arylsulfamoyl groups, etc .; as acyloxy groups, alkylcarbonyloxy groups, arylcarbonyloxy groups, etc .; as carbamoyloxy groups, alkylcarbamoyl groups. Xy group, arylcarbamoyloxy group, etc .; ureido group, alkylureido group, arylureido group, etc .; sulfamoylamino group, alkylsulfamoylamino group, arylsulfamoylamino group, etc .; as heterocyclic group Is preferably a 5- to 7-membered one, specifically, 2-furyl group, 2-thienyl group, 2-
Pyrimidinyl group, 2-benzothiazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole -5-oxy group and the like; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,
4-diphenoxy-1,3,5-triazole-6-thio group; as siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; as imide group, succinimide group, 3-heptadecyl Succinimide group, phthalimide group, glutarimide group, etc .; Spiro compound residues include spiro [3.3] heptan-1-yl, etc .; Bridged hydrocarbon compound residues include bicyclo [2.2.1] heptane-1- And tricyclo [3.3.1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The groups represented by R ₁₁ , R ₁₂ , R ₁ , R ₂ , and Ra include those having a substituent.

Examples of the group represented by X which can be split off by the reaction with the oxidation product of the color developing agent include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy,
Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples thereof include acylamino, sulfonamide, a nitrogen-containing heterocycle bonded by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, and the like, but a halogen atom, particularly a chlorine atom is preferable.

Also included in the invention are polymeric couplers and polymeric couplers such as dimeric couplers containing a pyrazolotriazole ring in R ₁ , R ₂ or X.

Further, the present invention also includes a compound having a group obtained by removing A from the compound represented by the general formula [I] in the residue represented by A in the general formula [I].

2 represented by L in the above general formula [I]
As the valent linking group, alkyl, aryl, anilino,
Acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Alkoxy, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino, alkylamino,
Imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
It represents a divalent group derived from an alkoxycarbonyl group, an aryloxycarbonyl group, or a heterocyclic thio group, and a divalent group that can be formed by combining these divalent groups, preferably a compound represented by the following general formula [X ] Is shown.

[0029]

[Chemical 5]

In the formula, the R ₁₃ side is bonded to the pyrazoloazole ring.

R ₁₃ , R ₁₄ and R ₁₅ in the general formula [X] are
Each independently represents an alkylene group having 1 to 12 carbon atoms, an arylene group, an alkylenearylene group or an aralkylene group. The alkylene group, which may be linear or branched, is, for example, a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, etc., and the arylene group is, for example, a phenylene group, a naphthylene group, etc., and an aralkylene group. As the alkylenearylene group,

[0032]

[Chemical 6]

And the like.

The alkylene group, arylene group, alkylenearylene group or aralkylene group represented by R ₁₃ , R ₁₄ and R ₁₅ may have a substituent, and the substituent may be any of R ₁₁ , R ₁₂ and R. Each substituent represented by ₁ , R ₂ and Ra can be mentioned.

Further, L ₁ , L ₂ and L in the general formula [X] are
₃ is

[0036]

[Chemical 7]

Represents However, R ₁₆ represents a hydrogen atom, an alkyl group or an aryl group, and when two R ₁₆ are present, each R ₁₆ may be the same or different. p, q, r, s, t and u represent an integer of 0 or 1.

The chain length of the linking group represented by -L- in the formula [I] is preferably 15 or less, more preferably 10 or less. When a ring structure moiety is present in the linking group, the number of atoms in the moiety is, for example, 3,0-in m-phenylene.
In phenylene, the number is counted along the path with the smallest number of atoms such as 2.

Typical examples of the magenta coupler according to the present invention will be shown below, but the present invention is not limited thereto.

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

The above-mentioned pyrazoloazole-based magenta coupler according to the present invention is described in Journal of the Chemical Society, Perkin; I (1977), 2047-2052, US Pat.
725,067, JP-A-59-99437, 59-171956, 60-4
No. 3659, No. 60-172982, No. 60-190779, New Experimental Chemistry Course Volume 14-III, pp. 1585-1594 (1977) Maruzen, Volume 14-III
1573 ~ 1584 (1977) Maruzen Helv. Acta, Vol. 36, 75 (195)
3), J. Am. Chem. Soc, Vol. 72, p. 2762 (1950), Org ・ Synt
It can be easily synthesized by those skilled in the art with reference to h.II, page 395 (1943) and the like.

Next, typical synthesis examples of the pyrazoloazole-based magenta coupler according to the present invention will be shown below.

Synthesis Example 1 Synthesis of Exemplified Compound ME-2 The synthetic route is shown below.

[0053]

[Chemical 18]

1 4.8 g of N, N-dimethylacetamide 20 ml
After heating and dissolving in acetonitrile, 100 ml of acetonitrile and succinic anhydride 2.0
g was added and the mixture was heated under reflux for 5 hours. After acetonitrile was distilled off under reduced pressure, the reaction solution and 200 ml of water were poured and the crystals separated were collected by filtration. The product was purified by silica gel column chromatography to give 24.6 g of white amorphous substance.
Got (The structure was confirmed by ¹ HNMR, FD mass spectrum, and IR.) Further, 24.5 g and 3 3.6 g were dissolved in 50 ml of 1.4-dioxane to prepare dicyclohexylcarbodiimide (DC).
C) 3.1 g was added and the mixture was stirred at room temperature for 4 hours. The insoluble matter was filtered off, 200 ml of ethyl acetate and 100 ml of water were added for extraction, and the product was further purified by washing with silica gel column chromatography to obtain 5.8 g of ME-2 in the form of a pale yellow extract. ( ¹ HNMR, FD
The structure was confirmed by mass spectrum and IR. ) It is preferable that the magenta coupler used in the present invention is contained in the silver halide emulsion.
A conventionally known method may be followed. For example, tricresyl phosphate, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate, or a low boiling point solvent such as ethyl acetate or butyl propionate is used alone or as a mixture thereof according to the present invention. The magenta coupler, alone or in combination, may be dissolved, mixed with an aqueous gelatin solution containing a surfactant, and then emulsified with a high-speed rotary mixer or a colloid mill, and then added to the silver halide emulsion.

The magenta coupler according to the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 mol, per mol of silver halide.
It can be used in the range of x10 ^-2 to 8 x 10 ^-1 mol.

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

The pyrazoloazole-based magenta coupler according to the present invention can be used in combination with the image stabilizer represented by the following general formula [A] and / or general formula [B].

[0058]

[Chemical 19]

In the general formula [A], R ₂₁ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Among them, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-octyl group, a tert-octyl group, a benzyl group and a hexadecyl group. A straight chain or branched alkyl group can be mentioned.

Examples of the alkenyl group represented by R ₂₁ include allyl, hexenyl and octenyl groups.

Further, examples of the aryl group of R ₂₁ include phenyl and naphthyl groups. Further, examples of the heterocyclic group represented by R ₂₁ include a tetrahydropyranyl group and a pyrimidyl group.

Each group represented by R ₂₁ includes one having a substituent.

In the general formula [A], R ₂₂ , R ₂₃ , R ₂₅
And R ₂₆ is a hydrogen atom, a halogen atom, a hydroxyl group,
It represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acylamino group. Of these, the alkyl group, the alkenyl group, and the aryl group are the same as the alkyl group, the alkenyl group, and the aryl group described above for R _21. Is mentioned.

Examples of the halogen atom include fluorine, chlorine and bromine atoms.

Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group and the like. Furthermore, the acylamino group is R ₂₇ -CONH-
Wherein R ₂₇ is an alkyl group (eg methyl, ethyl, n-propyl, n-butyl, n-octyl, te
rt-octyl, benzyl, etc.), alkenyl group (eg, allyl, octenyl, oleyl, etc.), aryl group (eg, phenyl, methoxyphenyl, naphthyl, etc.) or heterocyclic group (eg, pyridinyl, pyrimidyl) Each group of) can be represented.

In the general formula [A], R ₂₄ represents an alkyl group, a hydroxyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. Among them, the alkyl group and the aryl group are as described above. Specific examples thereof include the same ones as the alkyl group and aryl group represented by R ₂₁ . The alkoxy group for R ₂₄ may be the same as the alkoxy group described for R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ .

R ₂₁ and R ₂₂ may be ring-closed to each other to form a 5-membered or 6-membered heterocycle, and R ₂₃ and R ₂₄ may be ring-closed to form a 5-membered ring. Often, these rings 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.

[0069]

[Chemical 20]

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

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) 290
4 ~ 2914 (1965); The Journal of Organic Chemistr
y), Vol. 23, pp. 75-76; Tetrahedr
on) Vol. 26, 4743-4751 (1970); Chemical Letter (Chem, Lett), (4), 315-316 (1972); Journal of the Chemical Society of Japan, No. 10, 1987-1990 ( 1972); Journal of the Chemical Society
Chemical Society), pp. 415-417 (1962); Bourtin of Chemical Society of Japan, vol. 53, 555-556 (1980), etc. .

[0073]

[Chemical formula 23]

In the general formula [B], R ₃₁ is a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group,
It represents a cycloalkyl group or an aryl group, R ₃₂ represents a halogen atom, an alkyl group, an alkenyl 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 represents S, SO, SO ₂ or an alkylene group.

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. Specifically, t-butyl, s-butyl, t-amyl, s-amyl,
Examples thereof include groups such as t-octyl, i-propyl, i-propenyl, and 2-hexenyl.

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

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

The aryl group represented by R ₃₁ and R ₃₂ is preferably a phenyl group or a naphthyl group, specifically, phenyl, 4-nitrophenyl, 4-t-butylphenyl, 2,4-di-t.
-Amylphenyl, 3-hexadecyloxyphenyl, α-
Examples include naphthyl.

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, butylidene and hexamethylene.

Each group represented by R ₃₁ , R ₃₂ and Y ₁ may have a substituent.

Examples of the substituent which R ₃₁ , R ₃₂ and Y ₁ may have include a halogen atom and groups such as nitro, cyano, amide, sulfonamide, alkoxy, aryloxy, alkylthio, arylthio and acyl. Be done.

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

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

The compound represented by the general formula [B] is represented by US Pat. No. 2,807,653, Journal of the Chemicals.
Society Perkin I (J. Chem. Soc. Perkin
I) It can be synthesized according to the method described on page 1712 (1979).

The amount of the image stabilizer represented by the general formula [A] or the general formula [B] is 5 to 400, based on the pyrazoloazole-based magenta coupler of the present invention.
It is preferably mol%, more preferably 10 to 250
Mol%.

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

The silver halide composition preferably used in the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide.

The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, as silver halide.
Any of those used for ordinary silver halide emulsions such as silver chlorobromide, silver chloroiodobromide and silver chloride can be used.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain, or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The grain size of the silver halide grains is preferably 0.05 to 30 μm, more preferably 0.1 to 20 μm.

The silver halide emulsion having any grain size distribution can be used. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. The coupler used in the present invention includes a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent by coupling with a colored coupler having an effect of color correction and an oxidation product of a developing agent. Included are compounds that release photographically useful fragments such as agents, hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers. Of these, a so-called DIR compound which releases a development inhibitor with development and improves the sharpness of images and the graininess of images may be used.

In this DIR compound, the one in which the inhibitor is directly bonded to the coupling position and the one in which the inhibitor is bonded to the coupling position via the divalent group and which is separated by the coupling reaction A compound (referred to as a timing DIR compound) that is bound so as to release the inhibitor by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction is included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application.

A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with a dye-forming coupler.

Examples of yellow couplers preferably used in the present invention include known acylacetanilide type couplers. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds can be advantageously used.

Examples of cyan couplers preferably used in the present invention include phenol or naphthol couplers.

Between the emulsion layers of the light-sensitive material (the same color-sensitive layer and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. Also, a color antifoggant can be used to prevent the graininess from being conspicuous.

An image stabilizer which prevents deterioration of a dye image can be used in the light-sensitive material of the present invention. Compounds which can be preferably used are those described in Item VII J of RD17643.

A hydrophilic colloid layer such as a protective layer or an intermediate layer of the light-sensitive material contains an ultraviolet ray inhibitor in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like and to prevent deterioration of an image by ultraviolet rays. You can leave.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

The present invention can be preferably applied to color negative films, color papers, color reversal films and the like.

[0106]

EXAMPLES The present invention will now be described based on examples, but the embodiments of the present invention are not limited thereto.

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, titanium oxide was applied to each layer having the constitution shown in Tables 1 and 2 below. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic light-sensitive material sample 101 was prepared.

[0108]

[Table 1]

[0109]

[Table 2]

The coating solution was prepared as follows.

First layer coating liquid 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, ethyl acetate 60 cc. 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 in 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 coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

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

[0115]

[Chemical 27]

[0116]

[Chemical 28]

[0117]

[Chemical 29]

[0118]

[Chemical 30]

[0119]

[Chemical 31]

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 stabilizing agent STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-14 × 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-1 1 × 10 shows the structural formulas of the compounds used in each monodispersed cubic emulsion ^-4 mol / mol AgX.

[0121]

[Chemical 32]

Next, the third layer coupler EM-1 of Sample 101 was used.
Were replaced with equimolar couplers of the present invention shown in Table 3 below, and dye image stabilizers were further replaced as shown in Table 3 to prepare Samples 102 to 118.

The magenta coupler E used for the comparative sample
The structural formulas of M-2, EM-3 and EM-4 are EM described above.
Shown with -1.

The sample 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. Per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution 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'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Add water to bring the total volume to 1000 cc.
Is adjusted to 10.10 and the pH of the replenisher is adjusted to 10.60.

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. Water To 1,000 cc. And adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid (tank liquid and replenishing liquid are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1000 cc. Adjust the pH with sulfuric acid or potassium hydroxide. Adjust to 7.0.

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 7 days, and the residual ratio (%) of the dye image at the initial density of 1.0 was determined.

The results are shown in Table 3.

[0134]

[Table 3]

In Sample Nos. 101 to 106 of Table 3, the 6-position substituent is t-
It is a coupler which is a butyl group, and Sample Nos. 107 to 110 are 6
Sample No. 111 is a coupler in which the position substituent is a methyl group.
˜114 are couplers in which the 6-position substituent is an isopropyl group. Furthermore, sample Nos. 115 to 118 are 1H-pyrazolo [1,5-b] triazole type couplers, but when comparing these by type, it is clear that in any case, the sample of the present invention is significantly larger than the comparative sample. The improvement of light resistance was observed.

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

Example 2 Sample Nos. 201 to 220 were prepared by substituting the dye image stabilizers of the third layer of Sample No. 101 of Example 1 with the combinations shown in Table 4 below.
Was produced.

The same evaluation as in Example 1 was performed using the obtained sample. However, the light resistance was evaluated by the dye image residual rate after irradiation with a xenon fade meter for 12 days. The results are shown in Table 4.

[0139]

[Table 4]

From Table 4, even when the phenol-based dye image stabilizers (B-3 and A-24) were used in combination, the same tendency as in Example 1 was observed for all types (6-position t-butyl group, 6
Position-methyl, 6-position, isopropyl, 1H pyrazolo [1,5-b]
(Triazole), and the light resistance was further significantly improved as compared with the comparative sample. The color developability was equal to or higher than that of the comparative sample.

[0141]

The silver halide color photographic light-sensitive material containing the coupler of the present invention in which the amine-based dye image stabilizer is incorporated in the pyrazolotriazole-based magenta coupler has dramatically improved light resistance as compared with the conventional one. It has been found that it has an effect that it is improved and has very excellent image storability and also excellent in color development.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one magenta coupler represented by the following general formula [I]. [Chemical 1] [Wherein, A is R ₁ from the pyrazolotriazole magenta coupler represented by the following general formula (II) or formula (III)
Or it represents a residue obtained by removing the R ₂ L represents a divalent linking group or a single bond, or -O -, - S- or -N (Ra) -
R a represents a hydrogen atom or a substituent, R ₁₁ and R
₁₂ represents a hydrogen atom or a substituent, R ₁₁ and R ₁₂ may be the same or different, and may be condensed with each other to form a 5- to 7-membered ring. ] [Chemical 2] [Wherein R ₁ and R ₂ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]