JPH05323530A - Halogenized silver chromatic photosensitive material - Google Patents

Abstract

PURPOSE:To enhance the color reproductivity and the color development ability and to enhance the light toughness of a Magenta pigment image by adding a specific Magenta coupler. CONSTITUTION:A Magenta coupler is given by the structural formula I where A is a remaining group obtained by removing R<1>, R<2> or X from a pigment formation given by the formulas I, II, and L is a bivalent coupling group which is coupled to a benzene ring through the intermediary of a carbon atom, an oxygen atom or a nitrogen atom. Further, R1 and R2 are a hydrogen atom, an alkyl group, a cycloalkyl, an alkennyl group, an aryl group, an acyl group and a complex ring group, R3 is a group which may be substituted by a benzene ring, and (l) is an integer from 0 to 3. If (l) is more than 2, a plural number of R3 may be the same or different from each other, and further L may be coupled between R1, R2, and R3 or between the plurality of R3 so as to form a ring. In the formulas II, III, R<1> and R<2> are a hydrogen atom, and a substituent, and X is a group which can be separated through reaction upon an oxidant which is a color developing main 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 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.

[0005]

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 impaired remarkably. ..

[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.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a silver halide which is excellent in color reproducibility and color developability and in which the light fastness of a magenta dye image is remarkably improved. It is to provide a color photographic light-sensitive material.

[0010]

The above object of the present invention is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following general formula [I].

[0011]

[Chemical 3]

In the formula, A is the following general formula [II] or [III]
Represents a residue obtained by removing R ¹ , R ² or X from the dye-forming coupler represented by and L represents a divalent linking group bonded to the benzene ring via a carbon atom, an oxygen atom or a nitrogen atom.
R ₁ and R ₂ are a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an alkenyl group, an aryl group, an acyl group and a heterocyclic group, R ₃ represents a group capable of substituting for a benzene ring, and l represents an integer of 0 to 3. Here, when l is 2 or more, plural R ₃
May be the same or different, and L, R ₁ ,
R ₂ and R ₃ or a plurality of R ₃ may be bonded to each other to form a 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 in more detail below.

In the above general formulas [I], [II] and [III], the substituents represented by R ¹ , R ² and R ³ are not particularly limited, but are typically alkyl, aryl and anilino. , Acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, aryloxy, heterocyclic oxy,
Each group of siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, etc., and spiro compound residue And a bridged hydrocarbon compound residue.

The alkyl group represented by R ¹ , R ² and R ₃ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group, and the acylamino group includes an alkylcarbonylamino group, an arylcarbonylamino group and the like.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkylthio group represented by R ¹ , R ² and R ₃ and the alkyl component and aryl component in the arylthio group include the alkyl group and aryl group represented by R ¹ , R ² and R ₃ .

The alkenyl group represented by R ¹ , R ² and R ₃ is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

The sulfonyl group represented by R ¹ , R ² and R ₃ is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like; and the phosphonyl group is an alkylphosphonyl group. A nyl group, an alkoxyphosphonyl group,
Aryloxyphosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group , An arylsulfamoyl group, etc .; an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; an ureido group, an alkylureido group, Aryl ureido group, etc .; Sulfamoylamino group, alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group preferably has 5 to 7 members, specifically 2-furyl , 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferable, for example, 3,4,5,6-tetrahydropyranyl-2 -Oxy group, 1-phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, and examples thereof include 2-pyridylthio group, 2-benzothiazolylthio group, 2, 4-diphenoxy-1,3,5-triazole-6-thio group; siloxy groups such as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide groups such as succinimide group, 3-
Heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residues include spiro [3.3] heptan-1-yl and the like; bridged hydrocarbon compound residues include bicyclo [2.2. 1] heptane-1-yl, tricyclo [3.3.1.1 ^37] decane-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

The groups represented by R ¹ , R ² and R ₃ 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, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, N Examples thereof include nitrogen-containing heterocycles bonded by atoms, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

When l is 2 or more, a plurality of R _3's may be the same or different, and at that time, a plurality of R ₃ 's may form a condensed ring.

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 in which A is removed 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,
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. A benzene ring of the general formula [I] Represents a group linked to each other via a carbon atom, an oxygen atom or a nitrogen atom, and is preferably represented by the following general formula [X].

[0030]

[Chemical 5]

In the formula, the R ³ side is bonded to the pyrazoloazole ring.

R ³ , R ⁴ and R ⁵ in the general formula [X] each independently represent an alkylene group having 1 to 12 carbon atoms, an arylene group, an alkylenearylene group or an aralkylene group. The alkylene group may be linear or branched, but is, for example, a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, or the like, and as the arylene group,
For example, a phenylene group, a naphthylene group and the like, and as the aralkylene group and alkylenearylene group,

[0033]

[Chemical 6]

And the like.

The alkylene group, arylene group, alkylenearylene group or aralkylene group represented by R ³ , R ⁴ and R ⁵ may have a substituent, and the substituent is represented by R ¹ and R ² . Each of the above substituents is included.

L ¹ and L ² in the general formula [X] are

[0037]

[Chemical 7]

And L ³ is

[0039]

[Chemical 8]

Represents

However, R ⁶ represents a hydrogen atom, an alkyl group or an aryl group, and when two R ⁶ are present, each R ⁶ may be the same or different. p, q, r, s, t and u represent an integer of 0 or 1.

In the above general formula [I], the alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group represented by R ₁ and R ₂ are respectively represented by the above general formulas [II] and [III]. Examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and a heterocyclic group represented by R ¹ and R ² in, and these groups may further have a substituent. R ₁ and R ₂ are preferably alkyl groups.

In the above general formula [I], the group capable of substituting on the benzene ring represented by R ₃ is the above general formula [II]
And the substituents represented by R ¹ and R ² in [III]. R ₃ is preferably an electron-donating group having a Hammett's σp value of 0 or less (for example, an alkoxy group, an alkyl group, an amino group, etc.).

In the above general formula [I], R ₁ and R ₂ , R ₂
The ring formed by R ₃ and R ₃ , R ₃ and R ₁ or a plurality of R ₃ bonded to each other is preferably a 5- to 7-membered ring, for example,

[0045]

[Chemical 9]

And the like. These may further have a substituent.

Typical examples of the magenta coupler used in the present invention are shown below, but the present invention is not limited thereto.

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical formula 12]

[0051]

[Chemical 13]

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

Next, a synthesis example of the magenta coupler used in the present invention is shown.

Synthesis Example (Synthesis of Exemplified Compound 2) First, the synthetic route of the intermediate 7 is shown.

[0061]

[Chemical 21]

The synthetic route of Exemplified Compound 2 is as follows.

[0063]

[Chemical formula 22]

The synthesis method will be specifically described below.

I) Synthesis of Intermediate 1 51.2 g of β-alanine and 92.4 g of phthalic anhydride were placed in a 500 cc. Reactor and heated in an oil bath with a bath temperature of 160 ° C. for 1 hour. Ethanol (500 cc.) Was added to the molten reaction product, and after heating and dissolving,
After cooling to room temperature, crystals were precipitated. By filtering the crystals, 121.2 g of Intermediate 1 was obtained.

(Structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) II) Synthesis of Intermediate 4 Intermediate 3 (30.0 g) was mixed with chloroform 100 cc. And thionyl chloride.
After adding 20 cc. And heating under reflux for 3 hours, excess thionyl chloride and chloroform were distilled off under reduced pressure. (Yield 33.9 g) 27.0 g of this acid chloride and 20.9 g of Intermediate 3 were suspended in 350 cc. Of acetonitrile and heated under reflux.

The reaction mixture gradually dissolves and completely dissolves, but crystals start to precipitate again. If you continue heating and refluxing as it is, the crystals will gradually dissolve. After heating under reflux for 6 hours,
The insoluble matter was hot filtered, and the solvent acetonitrile was distilled off under reduced pressure. The brown oily matter obtained was recrystallized from methanol to obtain 25.5 g of pale yellow crystalline intermediate 4.

(Structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) III) Synthesis of Intermediate 5 125 cc. Of acetic anhydride was added to 25 g of Intermediate 4 and heated under reflux for 3 hours. After distilling off excess acetic anhydride at atmospheric pressure (about 100 cc.),
The reaction solution was cooled to room temperature. To this, 250 cc. Of methanol and 25 cc. Of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 2 hours.

After separating the precipitated sulfur by furnace, the methanol was distilled off under reduced pressure, and 200 cc. Of ethyl acetate and 100 cc. Of tetrahydrofuran were added, followed by neutralization with an aqueous sodium hydroxide solution. The organic phase was washed twice with 200 cc of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was recrystallized with a mixed solvent of acetonitrile / methanol = 1/1, to obtain 17.5 g of Intermediate 5.

(Structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) IV) Synthesis of Intermediate 6 17.5 g of Intermediate 5 was dissolved in 150 cc. Of tetrahydrofuran and then cooled in an ice bath to give 5 ℃ was made. To this reaction solution, 6.9 g of N-chlorosuccinimide (NCS) was added over about 2 hours. After reacting at 5 ℃ for 2 hours, add 100c
It was washed twice with the saline solution of c. The organic phase was dried over anhydrous magnesium sulfate, and the pale yellow oily product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography and then recrystallized from a mixed solvent of ethyl acetate / n-hexane. Thus, 16.5 g of white crystalline intermediate 6 was obtained.

(Structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) V) Synthesis of Intermediate 7 16.0 g of Intermediate 6 was dissolved by heating in 130 cc. Of ethanol, and then hydrazine monohydrate 3.23 g and 0.8 cc of water were added, and the mixture was heated under reflux for 3 hours. The solvent was distilled off under reduced pressure, 180 cc. Of water and 41.5 cc. Of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 1 hour. After cooling the reaction solution to room temperature and separating the precipitated by-product from the furnace,
The solvent water was distilled off under reduced pressure to obtain a yellow solid. Methanol (50 cc.) Was added to this solid and the mixture was stirred at 50 ° C. for 1 hour, insoluble materials were removed by filtration, and the obtained solution was concentrated. The obtained product was dissolved in 10 cc. Of methanol, and 40 cc. Of acetonitrile was added to recrystallize the product to obtain 9.2 g of a pale yellow crystalline intermediate 7.

(Structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) VI) Synthesis of Exemplified Compound 2 To 11.3 g of Intermediate 8, 200 cc. Of ethyl acetate and 200 cc. Of water were added to prepare an aqueous phase. The mixture was neutralized by adding dilute hydrochloric acid until the pH became 5 to 6, separated, and washed with 100 cc. of water. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give Intermediate 9,
10.6 g was obtained.

Then, 200 cc. Of tetrahydrofuran and 100 cc. Of saline were added to 9.2 g of the intermediate 7, and sodium hydrogencarbonate 2.
6 g was added and the layers were separated. After washing with 50 cc. Of saline, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain Intermediate 10 (7.1 g).

Intermediates 1 and 10.6 g thus obtained and intermediates 10 and 7.1
After dissolving g in 200 cc. of DMF, 6.6 g of N, N-dicyclohexanecarbodiimide was added and stirred at room temperature for 10 hours.
After being separated from the insoluble matter by filtration, the solution was poured into 500 cc. Of water, and the protruding solid was collected by filtration. The solid product was purified by silica gel column chromatography to obtain 8.1 g of Exemplified Compound 2 as white crystals.

(The structure was confirmed by ¹ H NMR spectrum, IR spectrum, and FD mass spectrum.) It is preferable to incorporate the magenta coupler used in the present invention into the silver halide emulsion. Just follow the method. 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 bottom 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 may be dissolved alone or in combination, then 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 coupler of the present invention can be used in the range of usually 1 mol of silver halide, 1 × 10 ^-3 to 1 mol, and preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol.

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

The couplers of this invention can be used in combination with various image stabilizers. Preferable image stabilizers include phenol compounds, phenyl ether compounds, amine compounds, chelate compounds, and the like. Exemplified compounds GG described in JP-A No. 62-215272, pp. 133-137. -1 to GG-54, the exemplified compounds (a-1) to (a- described in JP-A-4-95952, pages 23 to 29)
8), (b-1) to (b-6), (C-1) to (c-
7), IIIa-1 to IIIa-15, IV-1 to IV-22, V-1
To V-10 and VI-1 to VI-5, JP-A-60-262159, No. 11 to
Exemplified compounds A-1 to A-28 and 61-145 described on page 13
Exemplary compounds PH-1 to P described in No. 552, pages 8 to 10
H-29, exemplary compounds B-1 to B-21 described on pages 6 to 7 of JP-A-1-306846, and exemplary compounds I-1 to I described on pages 10 to 18 of 2-958. -13, I'-1 to I'-8, II-
1 to II-12, II'-1 to II'-21, III-8 to III-14,
IV-1 to IV-24, V-13 to V-17, No. 3-39956 No. 10-11
Exemplified compounds II-1 to II-33 described on page, JP-A 2-16
7543, compounds B-1 to B-65 described on pages 8 to 11;
Exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439 may be mentioned.

The amount of the image stabilizer used in combination with the coupler of the present invention is preferably 5 to 400 mol%, more preferably 10 to 10%, based on the pyrazoloazole-based magenta coupler of the present invention. It is 250 mol.

The pyrazoloazole-based 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 contains, as silver halide, silver bromide, silver iodobromide, silver iodochloride,
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 grains 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 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 suppressor, those which are diffusible after withdrawal and those which are 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 may be used in combination with the 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 type couplers.

Between the emulsion layers of the light-sensitive material (the same color-sensitive layers 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 that can be preferably used are those described in Item VII, J of RD17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material contain a UV 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 the image by UV 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.

[0097]

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 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. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic material sample 101 was prepared.

[0099]

[Table 1]

[0100]

[Table 2]

The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, 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.

[0106]

[Chemical formula 23]

[0107]

[Chemical formula 24]

[0108]

[Chemical 25]

[0109]

[Chemical formula 26]

[0110]

[Chemical 27]

[0111]

[Chemical 28]

Blue-sensitive silver halide emulsion (Em-B) Monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% Sodium thiosulfate 0.8 mg / mol AgX chloride Auric acid 0.5 mg / mol AgX stabilizing agent STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / Molar AgX Green-sensitive silver halide emulsion (Em-G) Monodisperse cubic cubic silver chlorobromide emulsion with average particle size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5 mol% Sodium thiosulfate 1.5 mg / mol AgX gold chloride 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) 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 chloride Acid 2.0 mg / mol AgX Stabilizing agent STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / compound used in the monodispersed cubic emulsion in mol AgX below The structural formula is shown.

[0113]

[Chemical 29]

Next, the third layer coupler EM-1 of Sample 101 was used.
Were replaced by 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 130.

The magenta coupler E used for the comparative sample
Structural formulas of M-2, EM-3, EM-4, EM-5 and EM-6 are shown together with EM-1 described above.

The thus-prepared sample 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 developer solution Tank replenisher 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 make the total volume 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 an initial density of 1.0 was determined.

The results are shown in Table 3.

[0126]

[Table 3]

The couplers used in Sample Nos. 101 to 107 in Table 3 are couplers in which the 6-position substituent is a t-butyl group,
Sample Nos. 108 to 115 are couplers in which the 6-position substituent is a methyl group or a substituted primary alkyl group, and Sample Nos. 116 to 12
2 is a coupler whose 6-position substituent is an isopropyl group. Furthermore, sample Nos. 123 to 130 are 1H-pyrazolo [1,5-b] triazole type couplers, but when comparing these by type, it is clear that in both cases, the light resistance is significantly higher than that of the comparative sample. The improvement was seen. Further, the known magenta couplers EM-5 and EM-6 having a dye image stabilizer in the molecule are significantly inferior in light resistance to the coupler of the present invention of the same type, and the effect of the coupler of the present invention is large. However, it became clear from this.

In each case, it was also confirmed that the coupler of the present invention has the same or higher color-forming property as compared with the comparative coupler.

Example 2 Sample Nos. 201 to 230 were prepared by replacing the dye image stabilizer of the third layer of Sample No. 101 of Example 1 with the combinations shown in Table 4 below.
Was produced. The structural formula of the dye image stabilizer ST-4 is shown together with ST-3 described above.

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.

[0131]

[Table 4]

From Table 4, even when the dye image stabilizers (ST-3 and ST-4) 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-isopropyl, 1H pyrazolo [1,5-b] triazole), and the light resistance was further improved. The color developability was equal to or higher than that of the comparative sample.

[0133]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material containing the coupler of the present invention in which a phenol-based dye image stabilizer is incorporated in a 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 containing a magenta coupler represented by the following general formula [I]. [Chemical 1] [Wherein A represents a residue obtained by removing R ¹ , R ² or X from the dye-forming coupler represented by the following general formula [II] or [III], and L represents a carbon atom, an oxygen atom or a nitrogen atom. It represents a divalent linking group bonded to the benzene ring via. R ₁ and R ₂ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acyl group and a heterocyclic group, R ₃ represents a group capable of substituting for a benzene ring, and l represents 0 to 3 Represents an integer. Here, when 1 is 2 or more, a plurality of R ₃ may be the same or different, and are bonded to each other between L, R ₁ , R ₂ and R ₃ or a plurality of R _3. You may form a ring. [Chemical 2] In the formula, R ¹ and R ² each 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. ]