JPH05158197A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve lightfastness of a dye image and to enhance its storage stability and its color reproducibility by incorporating a specified compound in a silver halide emulsion layer containing a specified magenta coupler. CONSTITUTION:The silver halide emulsion layer containing at least one of the pyrazolo[5,1-c][1,2,4]triazole type magenta coupler represented by formula I contains at least one of the compounds represented by formulae II and III, and in formulae I-III, R1 is alkyl, aryl, alkoxy, or the like; (n) is 1 or 2; R is an aliphatic group; X is H, Cl, Br, alkoxy, or the like, or an N-containing heterocyclic group combined through the N atom; R21 is H, alkyl, aryl, a heterocyclic group, or the like; each of R22-R26 is H, halogen, or the like; R31 is an aliphatic or aromatic group; and Y is a nonmetallic atomic group necessary to form an N-containing 5- or 6-membered ring together with the N atom.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material excellent in image storability and color reproducibility.

[0002]

2. Description of the Related Art Conventionally, a combination of a yellow coupler, a magenta coupler and a cyan coupler is used in a color photographic paper which is directly provided for viewing. Many efforts have been made to date to improve the fastness of color dye images obtained from these couplers and to preserve and continue to utilize them for many years.

However, it is still not sufficient to meet the user's desire to prevent fading and discoloration of dye images in color photographs and to store high quality images semipermanently. In terms of storability in dark places such as albums, in recent years, significant improvements have been made as represented by "Konica Color 100 Years Print", and it has become possible to store photographic images for a long time that is satisfactory. On the other hand, the storage stability under the light (light resistance) under the condition of being exposed to light is still at an insufficient level, and improvement is desired. In particular, among the three color dyes of yellow, magenta, and cyan, the magenta dye has the weakest light resistance, and efforts have been made to improve it.

Further, the recently developed pyrazoloazole-based magenta couplers are different from 5-pyrazolone-based magenta couplers that have been conventionally used, and since the coloring dye has no secondary absorption around 430 nm, basically the color reproducibility is improved. It is known that the magenta dye obtained from the pyrazoloazole-based magenta coupler is inferior in light resistance to the magenta dye obtained from the 5-pyrazolone-based magenta coupler, though it is characterized by being advantageous to However, many improved techniques have been proposed. For example, JP-A-56-1
59644, 59-125732, 61-145552, 60-262159
No. 61-90155, JP-A-3-39956 and the like, and phenol or phenyl ether compounds, JP-A-61
-73152, 61-72246, 61-189539, 61-189540
Nos. 63-95439 and the like amine compounds, JP-A-61-140941, 61-145554, 61-158329, 62-
It is possible to use the metal complexes described in 183459, etc., the inclusion compounds described in JP-A No. 2-100048, the heterocyclic compounds and the like. However, when these compounds are used, the color density of the coupler is lowered, color contamination occurs during storage over time, color contamination occurs due to coloring of the added compound itself, and an undesirable change in color tone is caused. Or, the dispersibility of the dispersion containing the coupler may deteriorate, and the stability over time may deteriorate. Further, although the above-mentioned improved technology shows a great effect in improving the light resistance, the light resistance of the magenta dye is nevertheless improved. Is currently inferior to the light resistance of yellow dyes and cyan dyes, and as a result, the color balance of the image is disrupted during the fading process, causing the colors of the photograph to shift toward yellow and cyan, causing unnatural discoloration. There is a problem that it ends up. Further, a technique for improving light resistance by substituting a branched alkyl group having a large steric hindrance to the pyrazolotriazole skeleton is proposed in JP-A-61-65245 and the like, but in this case, light resistance is improved. There arise problems such as broad absorption of the generated dye and deterioration of color developability. Therefore, in order to improve the light resistance, it is strongly desired to develop a new technology.

[0005]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide color photographic light-sensitive material which has improved light resistance of dye images and excellent image storability. A second object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility.

[0006]

The above object of the present invention is to provide a compound represented by the following general formula [I]
And a pyrazolo [5,1-c] [1,2,4] triazole-based magenta coupler represented by the following formula.

[0007]

[Chemical 5]

[In the formula, R ₁ represents each group of alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, anilino, acylamino, etc., n represents 1 or 2, and R represents an aliphatic group. The aliphatic group may be further substituted with another substituent.

X is a hydrogen atom, a chlorine atom, a bromine atom,
It represents each group such as alkoxy, aryloxy, heterocyclic oxy, alkylthio, arylthio, heterocyclic thio, amino, acylamino, sulfonamide and the like and a nitrogen-containing heterocyclic group bonded by N atom. More preferably, the halogenated silver halide emulsion layer containing the magenta coupler represented by the general formula [I] contains at least one compound represented by the following general formula [II] or the general formula [III]. Made of silver color photographic light-sensitive material.

[0010]

[Chemical 6]

[In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0012]

[Chemical 7]

Here, R ₂₁ a, R ₂₁ b and R ₂₁ c each represent a monovalent organic group. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆
Each represents a hydrogen atom, a halogen atom, or a group capable of substituting for a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- or 6-membered ring. ]

[0014]

[Chemical 8]

[In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring with a nitrogen atom. The present invention will be described more specifically below.

The alkyl group represented by R ₁ may be linear, branched or cyclic, and may be substituted with another substituent, for example, methyl, ethyl, isopropyl or t-butyl. Group, neopentyl group, chloromethyl group, methoxymethyl group and the like.

The aryl group represents a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and they may be substituted with other substituents, for example, phenyl group, 2-chlorophenyl group, 4-methoxy group. Examples thereof include a phenyl group and a 1-naphthyl group.

As the alkoxy group, for example, a methoxy group,
Examples thereof include an ethoxy group, an isopropyloxy group, a cyclohexyloxy group and an ethoxyethoxy group.

Examples of the aryloxy group include a phenoxy group, a 2-methoxyphenoxy group, a 2-chlorophenoxy group, a 4-nitrophenoxy group and the like.

Examples of the alkylthio group include a methylthio group, a dodecylthio group and an isopropylthio group.

Examples of the arylthio group include a phenylthio group, a 2-butoxy-5-t-octylphenylthio group, a 4-chlorophenylthio group and the like. Examples of the anilino group include 2-chloroanilino group, 2-methoxyanilino group,
4-hibiloxyanilino group and the like can be mentioned.

Examples of the acylamino group include benzoylamino group, acetylamino group and pivaloylamino group.

Among the substituents represented by R ₁ , preferred is an alkyl group, and even more preferred is a branched alkyl group.

The aliphatic group represented by R may be linear, branched or cyclic and may be saturated or unsaturated. Further, this aliphatic group may be substituted with another substituent, and the substituent is not particularly limited, but typically, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cyclo Examples of each group such as alkyl, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy. , Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, each group such as heterocyclic thio, A spiro compound residue Rabbi, bridged hydrocarbon compound residue and the like are also mentioned.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

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

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R ₁ .

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Examples of the sulfonyl group include an alkylsulfonyl group, an arylsulfonyl group and the like;
As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; as the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, Arylcarbonyl group, etc .; carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; Acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc. Groups etc .; as carbamoyloxy groups, alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc .; as ureido groups, alkylureido groups, arylureido groups, etc .; sulfamoylamido The alkyl sulfamoylamino group, an aryl sulfamoylamino group group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-
Furyl group, 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, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole -6-thio group; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group Etc .; as the spiro compound residue, spiro [3.
3] heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.
3.1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Examples include heptan-1-yl and the like.

Among the aliphatic groups represented by R, the preferred ones are those having a total carbon number of 4 to 42 and further containing a branch.

Examples of the alkoxy group represented by X include a methoxy group, an isopropyloxy group and a cyclohexyloxy group.

Examples of the aryloxy group include phenoxy group, 2-nitrophenoxy group, 1-naphthyloxy group and the like.

Examples of the heterocyclic oxy group include a 3-pyridyloxy group and a 2-pyrazolyloxy group. Examples of the alkylthio group include n-octylthio group and 3-carboxyethylthio group.

Examples of the arylthio group include p-tolylthio group and 2-butoxyphenylthio group.

Examples of the heterocyclic thio group include 1-phenyl
Examples include -5-tetrazolylthio group and 2-pyridylthio group.

Examples of the amino group include a dipropylamino group, a morpholino group, a pyrrolidinyl group and the like.

Examples of the acylamino group include an acetylamino group and a benzoylamino group.

Examples of the sulfonamide group include a methanesulfonamide group and a p-toluenesulfonylamino group.

As the nitrogen-containing heterocycle bonded by N atom,
Examples thereof include a 1-imidazolyl group, a 1-pyrazolyl group, a 2-benzotriazolyl group and the like.

A chlorine atom is more preferable among the above substituents.

The typical examples of the magenta couplers according to the present invention are shown below, but the present invention is not limited thereto.

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

The synthesis examples of the compound of the present invention are shown below.

[Synthesis Example] Synthesis of Exemplified Compound 14 I) Synthetic Route

[0054]

[Chemical 18]

II) Synthesis of Intermediate 1 51.2 g of β-alanine and 92.4 g of phthalic anhydride were placed in a 500 ml reactor and heated in an oil bath with a bath temperature of 160 ° C. for 1 hour. To the molten reaction product, 300 ml of water and 50 ml of ethanol were added, dissolved by heating, and then cooled to room temperature to precipitate crystals. 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.) III) Synthesis of Intermediate 4 Intermediate 1 and 30.0 g were mixed with 100 ml of chloroform and thionyl chloride.
After adding 20 ml 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 ml of acetonitrile and heated to 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.) IV) Synthesis of Intermediate 5 125 ml of acetic anhydride was added to 25 g of Intermediate 4, and the mixture was heated under reflux for 3 hours. After distilling off excess acetic anhydride at atmospheric pressure (about 100 ml),
The reaction solution was cooled to room temperature. To this, 250 ml of methanol and 25 ml of concentrated hydrochloric acid were added, and the mixture was heated under reflux for 2 hours.

After the precipitated sulfur was separated by furnace, methanol was distilled off under reduced pressure, 200 ml of ethyl acetate and 100 ml of tetrahydrofuran were added, and the mixture was neutralized with an aqueous sodium hydroxide solution. The organic phase was washed twice with 200 ml of water and 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.) V) Synthesis of Intermediate 6 17.5 g of Intermediate 5 was dissolved in 150 ml of tetrahydrofuran and then cooled in an ice bath at 5 ° C. And To this reaction solution, 6.9 g of N-chlorosuccinimide (NCS) was added over about 2 hours. After reacting at 5 ℃ for 2 hours, 100ml of reaction mixture
It was washed twice with the saline solution. 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.) VI) Synthesis of Intermediate 7 16.0 g of Intermediate 6 was dissolved by heating in 130 ml of ethanol, and then 3.23 g of hydrazine monohydrate. And 0.8 ml of water were added and the mixture was heated under reflux for 3 hours. The solvent was distilled off under reduced pressure, 180 ml of water and 41.5 ml 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. To this solid was added 50 ml of methanol 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 ml of methanol, and 40 ml of acetonitrile was added to recrystallize it 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.) VII) Synthesis of Exemplified Compound 1 Intermediate 7, 5.0 g of dimethylacetamide (DMAc) 2
After heat-dissolving in 0 ml, 50 ml of acetonitrile was added, and further 15 ml of triethylamine was added, followed by cooling with an ice bath to bring the reaction solution temperature to 5 ° C. Intermediate 8 and a 3.5 g acetonitrile solution were added dropwise thereto over about 1 hour, and the mixture was stirred at room temperature for 2 hours. 100 ml of water and 300 m of ethyl acetate were added to the reaction product.
After adding l, it was neutralized with hydrochloric acid. The organic phase was washed twice with 100 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography to obtain white amorphous compound 14 (6.0 g).

(The structure was confirmed by ¹ H NMR spectrum, IR spectrum and FD mass spectrum.) The compound represented by the above general formula [II] or [III] was added to the silver halide emulsion layer containing the coupler of the present invention. It is preferable that at least one is contained.

In the above-mentioned general formula [II], the alkyl group, aryl group and heterocyclic group represented by R ₂₁ are explained as the alkyl group and aryl group represented by R ₁ in the above-mentioned general formula [I]. Groups. 5 as a heterocycle
It is preferably a 7-membered one, and specific examples thereof include a 2-furyl group, a 2-ethynyl group, a 2-pyrimygel group, and a 2-benzothiazolyl group. Examples of the monovalent organic group represented by R ₂₁ a, R ₂₁ b and R ₂₁ c include an alkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom.
R ₂₁ is preferably a hydrogen atom or an alkyl group. R ₂₂ ~
Examples of the group capable of substituting on the benzene ring represented by R ₂₆ include the groups described as the substituent represented by R ₁ in the general formula [I]. R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ are preferably a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or an acylamino group, and R ₂₄ is an alkyl group, a hydroxy group, an aryl group or an alkoxy group. Groups, aryloxy groups are preferred.
R ₂₁ and R ₂₂ may be ring-closed to each other to form a 5- or 6-membered ring, and R ₂₄ at that time is preferably a hydroxy group, an alkoxy group or an aryloxy group. R ₂₁ and R ₂₂ may be closed to form a methylenedioxy ring. Further, R ₂₃ and R ₂₄ may be closed to form a 5-membered hydrocarbon ring, and at that time, R ₂₁ is preferably an alkyl group, an aryl group or a heterocyclic group.

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

[0066]

[Chemical 19]

In addition to the above specific examples, specific examples of the compound represented by the general formula [II] include Exemplified Compound A described on pages 11 to 13 of JP-A-60-262159. -1 to A
-28, the exemplified compounds PH-1 to PH-29 described on pages 8 to 10 of JP-A 61-145552, and the exemplified compounds described on pages 6 to 7 of JP-A-1-306846. B-1 to B-2
1. Exemplified compounds I-1 to I-13, I'-1 to I'-8, II-1 to II- described on pages 10 to 18 of JP-A 2-958.
12, II'-1 to II'-21, III-8 to III-14, IV-1 to I
Examples thereof include V-24, V-13 to V-17, and the exemplified compounds II-1 to II-33 described on pages 10 to 11 of JP-A 3-39956.

Next, in the general formula [III], R ₃₁
Represents an aliphatic group or an aromatic group, preferably an alkyl group, an aryl group or a heterocyclic group, and most preferably an aryl group. Examples of the heterocycle formed by Y together with the nitrogen atom include a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1,1-dione ring and a pyrrolidine ring.

Specific examples of the compound represented by the general formula [III] are shown below.

[0070]

[Chemical 20]

In addition to the above specific examples, the above general formula [III]
Specific examples of the compound represented by: are exemplified compounds B-1 to B described on pages 8 to 11 of JP-A-2-167543.
-65, the exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439, and the like.

The amount of the compound represented by the general formula [II] or [III] added is 5 to 50 with respect to the coupler of the present invention.
0 mol% is preferable, and 20 to 200 mol% is more preferable.

Further, in the silver halide emulsion layer containing the coupler of the present invention and the non-color forming compound of the present invention, JP-A-61-158 is used.
The metal chelate compounds described in Nos. 329 and 62-183459 may be used. In order to incorporate the magenta coupler used in the present invention into the emulsion, a conventionally known method may be used. For example, the boiling point of tricresyl phosphate, dibutyl phthalate, etc. is 17
After dissolving the magenta coupler according to the present invention alone or in combination with a high-boiling point organic solvent having a boiling point of 5 ° C. or higher or a low-boiling point solvent such as ethyl acetate or butyl propionate, respectively or in a mixed solution thereof, if necessary. A silver halide emulsion for use in the present invention can be prepared by mixing with a gelatin aqueous solution containing a surfactant and then emulsifying with a high-speed rotary mixer or a colloid mill and then adding to a silver halide.

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

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

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 is a conventional silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Any of the above 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 .mu., And more preferably 0.1 to 20 .mu ..

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 couplers used in the present invention include a development inhibitor, a development accelerator, a bleaching accelerator, a developer and a silver halide solvent by coupling with a colored coupler having a color correcting effect and an oxidized product of a developing agent. , Toning agents, hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers, which release photographically useful fragments. 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 inhibitor is directly bonded to the coupling position, and the inhibitor is bonded to the coupling position via a divalent group. 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 also 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.

The 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.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material contain an anti-ultraviolet agent 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 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.

The color negative film, the color paper and the color reversal film are generally composed of a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer. There are no restrictions on the arrangement of the layers.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is carried out after exposure.

The color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilizing processing step if necessary, and a processing step using a bleaching solution and a processing using a fixing solution. Instead of the steps, the bleach-fixing treatment step can be carried out using a one-bath bleach-fixing solution, or the monobath treatment step using the one-bath developing bleach-fixing solution can be carried out for color development, bleaching and fixing. ..

[0096]

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 light-sensitive material sample 101 was prepared. 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, 0.67 g of stain inhibitor (HQ-1) and 6.67 g of high boiling organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was added with 20 ml of surfactant (SU-2) 10 ml. % Gelatin aqueous solution 220 ml was emulsified and dispersed using an ultrasonic homogenizer 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 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.

[0101]

[Table 1]

[0102]

[Table 2]

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

[0104]

[Chemical 21]

[0105]

[Chemical formula 22]

[0106]

[Chemical formula 23]

[0107]

[Chemical formula 24]

[0108]

[Chemical 25]

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodispersed cubic emulsion with average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5 mol% Sodium thiosulfate 0.8 mg / mol AgX chloroauric 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 / mol AgX green-sensitive Silver halide emulsion (Em-G) Monodisperse cubic emulsion with average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5 mol% Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stability Agent 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, Monodisperse cubic emulsion with a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer The structural formula of the TAB-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.

[0110]

[Chemical formula 26]

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 to prepare Samples 102 to 123.

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 ml per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution tank solution Replenishing solution Pure water 800 ml 800 ml 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 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, adjust the total volume to 1000 ml, adjust the pH of the tank solution to 10.10, and adjust the pH of the replenisher solution to 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water Adjust the total volume to 1000 ml, 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 Water is added to bring the total volume to 1000 ml, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

The following evaluations were performed using the sample after the continuous treatment.

<Light resistance> The obtained sample was irradiated with a xenon fade meter for 14 days, and the residual ratio (%) of the dye image at the initial density of 1.0 was determined.

Λmax: The maximum absorption wavelength of the wedge at a reflection optical density of 1.0.

Abs600: Absorbance at 600 nm of a wedge at a reflection optical density of 1.0 (the absorbance at λmax is 1.0).

Dmax: represents the maximum color density.

The results are shown in Table 3.

[0124]

[Table 3]

As is apparent from Table 3, a sample using a coupler in which the 6-position substituent of the magenta coupler is a t-butyl group
101 to 110, a sample 102 using the coupler of the present invention.
The samples Nos. To 110 have substantially the same color-developing properties as those of the comparative sample 101, but the light resistance is greatly improved, the absorbance at 600 nm is further reduced, and the color reproducibility is improved. Among Samples 111 to 117 using couplers having a methyl group as the 6-position substituent, Sample 112 using coupler EM-4 having a phenolic hydroxyl group in the 3-position substituent is more light-fast and color-developing than Comparative Sample 111. However, the absorption waveform of the dye becomes broad, the absorbance at 600 nm increases, and the color reproducibility deteriorates. On the other hand, Samples 113 to 116 using the coupler of the present invention show a large improvement in light resistance and 600 nm.
A decrease in absorbance was observed. Incidentally, in EM-5 (containing N-alkylacylamino group) (Sample 117) having a structure similar to that of the coupler of the present invention, almost no improvement effect in light resistance and color reproducibility was recognized. From this, the reason why the sample using the coupler of the present invention is excellent in light resistance and color reproducibility is that the five-membered group between the imino nitrogen at the 2-position of the dye and the amino hydrogen of the acylamino group (general formula) is used. It is considered to be due to an intramolecular hydrogen bond of [I] when n = 1) or a 6-membered (when n = 2 in the general formula [I]). (In the case of EM-5, an intramolecular hydrogen bond cannot be formed because the amino hydrogen of the acylamino group is substituted with an alkyl group.) In addition, Sample 118 using a coupler in which the 6-position of the coupler is an isopropyl group Similar results were obtained with 123 as well.

Example 2 Samples 201 to 216 were prepared by replacing the dye image stabilizer in the third layer of Sample 101 of Example 1 with the combinations shown in Table 4 below.

The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 4.

[0128]

[Table 4]

As is clear from Table 4, in any case where the 6-position of the magenta coupler is a t-butyl group, an isopropyl group or a methyl group, the use of the coupler of the present invention greatly improves the light resistance. It was confirmed that the color reproducibility was improved. Particularly, in light resistance, it was found that the effect is increased by using two kinds of the dye image stabilizers of the invention together.

[0130]

It has been found that the silver halide color photographic light-sensitive material of the present invention has excellent effects on image storability and color reproducibility.

Claims (2)

[Claims] 1. A silver halide color photograph containing at least one pyrazolo [5,1-c] [1,2,4] triazole magenta coupler represented by the following general formula [I]. Photosensitive material. [Chemical 1] [In the formula, R ₁ is alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, anilino,
Represents each group such as acylamino, n represents 1 or 2, and R
Represents an aliphatic group, and this aliphatic group may be further substituted with another substituent. X represents a hydrogen atom, a chlorine atom, a bromine atom, alkoxy, aryloxy, heterocyclic oxy, alkylthio, arylthio, heterocyclic thio, amino, acylamino, sulfonamide or the like, or a nitrogen-containing heterocyclic group bonded by an N atom. Represent ] 2. A silver halide emulsion layer containing a magenta coupler represented by the general formula [I] containing at least one compound represented by the following general formula [II] or general formula [III]. Item 1. A silver halide color photographic light-sensitive material according to Item 1. [Chemical 2] [In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue. [Chemical 3] Here, R ₂₁ a, R ₂₁ b and R ₂₁ c each represent a monovalent organic group. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, a halogen atom or a group capable of substituting for a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- or 6-membered ring. ] [Chemical 4] [In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Y represents a nonmetallic atom group necessary to form a 5- to 7-membered ring together with a nitrogen atom. ]