JPH05313326A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material improved in lightfastness of a color image and superior in storage stability of an image by incorporating a specified compound pyrazolotriazole-derived magenta coupler in a silver halide emulsion layer. CONSTITUTION:The silver halide color photographic sensitive material contains the pyrazolotriazole-derived magenta coupler represented by formula I or II in which each of R1-R8 is alkyl, and each of X and Y is H or a group to be released by coupling with the oxidation product of a color developing agent. This photosensitive material is imagewise exposed and developed with an aromatic primary amine color developing agent, thus permitting this magenta coupler to couple with the oxidation product of a developing agent and a magenta dye superior in lightfastness to be formed.

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 has been used for direct 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]
Alternatively, it is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one pyrazolotriazole type magenta coupler represented by the general formula [II].

[0007]

[Chemical 5]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ and R ₈ each represent an alkyl group, and X and Y each represent a hydrogen atom or a group capable of splitting off in association with the oxidation product of the color developing agent. ] More preferably, the formula [I] or the formula [I
A silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula [III] or [IV] in the silver halide emulsion layer containing a magenta coupler represented by ..

[0009]

[Chemical 6]

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

[0011]

[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. ]

[0013]

[Chemical 8]

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

The alkyl group represented by R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ may be linear, branched or cyclic, and may be substituted with another substituent. well,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a neopentyl group, a chloromethyl group, a hydroxymethyl group and a methoxymethyl group.

Among the substituents represented by R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ , preferred is an alkyl group, and more preferred is a methyl group.

The alkyl group represented by R ₄ and R ₈ may be linear, branched, or cyclic, and may be substituted with another substituent, and preferably has 1 to 32 carbon atoms.

Examples of the group represented by X and Y and capable of splitting off upon reaction with the oxidation product of the color developing agent include, for example, 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, acylamino, sulfonamide, nitrogen-containing N-bonded Examples thereof include heterocyclic groups, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

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

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical formula 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

Known couplers of the present invention are disclosed in, for example, JP-A-63 / 1988.
It can be synthesized according to the synthetic method described in No. 64046.

The synthetic examples of the compounds of the present invention are shown below.

[Synthesis Example] Synthesis of Exemplified Coupler 1

[0029]

[Chemical 15]

Synthesis of (B) To 91.1 g of (A) 500 ml of toluene and sodium methylate
135.0 g of 28% methanol solution was added, and the mixture was heated with stirring and about 200 ml of the solvent was distilled off under normal pressure. Further, 500 ml of toluene was added and the solvent was distilled off until the distillation temperature reached 110 ° C (about 340 m
l). After cooling to below 50 ℃, (t) -butylacetic acid chloride (bp127 synthesized from t-butylacetic acid and thionyl chloride)
℃ -131 ℃) 94.2g was added dropwise. After stirring at 85 ° C for 1 hour, the temperature was returned to room temperature, 135.0 g of sodium methylate 28% methanol solution was added, and the mixture was stirred for 1 hour. After leaving it overnight
Acidify with hydrochloric acid and extract with ethyl acetate.
After washing with water twice, the solution was concentrated under reduced pressure. Then, distillation was carried out under reduced pressure to obtain 37.9 g (32%) of (B). bp 90 ~ 105 ℃ / 23mmH
g.

Synthesis of (D) 190 ml of chloroform was added to 37.4 g of (B), cooled to 7 to 10 ° C., and 33.8 g of sulfuryl chloride was added dropwise. After dropping, at room temperature 3
After stirring for 0 minutes, the mixture was concentrated under reduced pressure, and (C) 42.2
g, ethanol (4.0N) that absorbed hydrogen chloride gas 54.3
ml and ethanol 550 ml were added and the mixture was heated under reflux for 6 hours.
After that, the mixture was cooled to room temperature, the crystals that were protruding were filtered, and the filtration was concentrated under reduced pressure. Ethyl acetate and aqueous sodium carbonate solution were added to the residue to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 23.9 g (35%) of (D).

Synthesis of (E) (D) 23.0 g of ethanol 400 ml of hydroxylamine
Add 38.6 g of 50% aqueous solution and heat to reflux for 3 hours, then
The mixture was cooled to room temperature, the protruding crystals were filtered, and the filtrate was concentrated under reduced pressure. Add ethyl acetate and water to the residue and p
H: 7-8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was recrystallized with a toluene / ligroin solvent to obtain 8.6 g (52%) of (E).

Synthesis of (G) To 8.5 g of (E), 30 ml of an aqueous solution in which 50 ml of ethyl acetate and 3.1 g of sodium acetate were dissolved was added and suspended, to which 15.3 of (F) was added.
g was added and the mixture was stirred at room temperature for 2 hours. The aqueous layer was removed, the ethyl acetate layer was washed twice with hot aqueous potassium hydrogen carbonate solution, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain (G) (19.4 g, 98%).

Synthesis of [H] To 18.5 g of (G) was added 350 ml of phosphorus oxychloride, and the mixture was heated under reflux for 1 hour and a half. Then, the mixture was concentrated under reduced pressure, an aqueous solution of potassium hydrogen carbonate in ethyl acetate was added to the residue to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue is purified by silica gel column chromatography, [H]
16.5 g (92%) was obtained.

Synthesis of [I] To 15.0 g of [H] was added 15 ml of concentrated sulfuric acid, 15 ml of water and 45 ml of acetic acid,
The mixture was heated under reflux for 9 hours. After cooling to room temperature, cool the reaction mixture with ice water.
Crystals poured into 0 ml were filtered. The residue was recrystallized from acetonitrile to obtain [I] (10.2 g, 77 g).

Synthesis of Exemplified Coupler 1 To 9.0 g of [I], 150 ml of chloroform and 25 ml of N, N-dimethylformamide were added and stirred at room temperature. 2.7 g of N-chlorosuccinimide was added little by little to the mixture, and the whole was added, followed by stirring at room temperature for 1 hour. Thereafter, the mixture was concentrated under reduced pressure, ethyl acetate and water were added to the residue to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 8.6 g (89%) of Exemplified Coupler 1. The structures of these compounds were confirmed by NMR, IR and mass spectra.

Other couplers according to the present invention can also be synthesized by a method similar to the above synthesis method.

It is preferable that the silver halide emulsion layer containing the coupler of the present invention contains at least one of the compounds represented by the above formula [III] or [IV].

In the above general formula [III], the alkyl group represented by R ₂₁ is the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R in the above general formula [I] or [II]. _The groups described as the alkyl group represented by ₇ and R ₈ can be mentioned. The aryl group and heterocyclic group represented by R ₂₁ are not particularly limited,
The aryl group is preferably a phenyl group, and the heterocyclic group is preferably a 5- to 7-membered one. Specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyridinyl group, and a 2-benzothiazolyl group. Be done.

Examples of the monovalent organic group represented by R ₂₁ a, R ₂₁ b and R ₂₁ c include alkyl groups, aryl groups, alkoxy groups, aryloxy groups and halogen atoms.
R ₂₁ is preferably a hydrogen atom or an alkyl group. R ₂₂ ~
Examples of the group capable of substituting the benzene ring represented by R ₂₆ include a hydrogen atom, hydroxy, alkyl, alkenyl, cycloalkyl, aryl, heterocycle, acylamino, halogen atom, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, cyano, alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, amino, anilino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbamoylamino, aryloxysulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, arylsulfonyl, alkylthio, arylthio, heterocyclicthio , Carboxyl and the like.

As R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ , a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an acylamino group are preferable, and R ₂₄ is an alkyl group and a hydroxy group. , Aryl groups, alkoxy groups, aryloxy groups, arylthio groups, and arylsulfonyl groups are preferable.

R_{twenty one}And R_{twenty two}Are closed to each other and have 5 or 6 members
May form a member ring, and R at that time _{twenty three}Or R_{twenty four}Is hydro
An oxy group, an alkoxy group, and an aryloxy group are preferable.
Also R_{twenty one}And R_{twenty two}Closed to form a methylenedioxy ring
May be. Furthermore, R_{twenty three}And R_{twenty four}Closed and five-member charcoal
A hydrogen atom ring may be formed, and R at that time is formed._{twenty one}Is a hydrogen atom,
An alkyl group, an aryl group and a heterocyclic group are preferable.

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

[0044]

[Chemical 16]

[0045]

[Chemical 17]

In addition to the above specific examples, the above general formula [III]
Specific examples of the compound represented by: JP-A-60-262159
Exemplified Compounds A-1 to 1 described in pages 11 to 13 of the publication
A-28, the exemplified compounds PH-1 to PH-29 described on pages 8 to 10 of JP-A 61-145552, and the examples described on pages 6 to 7 of JP-A-1-306846. Compounds B-1 to B-
21, 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
~ IV-24, V-13 to V-17, No. 3-39956, page 10 to 1
Exemplified compounds II-1 to II-33 described on page 1 may be mentioned.

Next, in the above general formula [IV], R ₃₁ represents an aliphatic group or an aromatic group, preferably an alkyl group,
An aryl group and a heterocyclic group are preferred, and an aryl group is most preferred. Examples of the heterocycle formed by Z 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 [IV] are shown below.

[0049]

[Chemical 18]

In addition to the above specific examples, specific examples of the compound represented by the above general formula [IV] include Exemplified Compound B-described on pages 8 to 11 of JP-A-2-167543. 1-B-
65, exemplary 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 [III] or [IV] 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 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 couplers used in the present invention include a colored coupler having a color correcting effect and a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent by coupling with 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 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 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.

The 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 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 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.

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 performed 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. ..

[0076]

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 26.7 g of yellow coupler (EY-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
60 ml of ethyl acetate was added to 6.67 g, 0.67 g of stain inhibitor (HQ-1) and 6.67 g of high boiling organic solvent (DNP) to dissolve, and this solution was dissolved in 7 ml of 20% surfactant (SU-2).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing the above 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. Below, Table 1,
Table 2 shows each configuration in detail.

[0081]

[Table 1]

[0082]

[Table 2]

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

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

[0088]

[Chemical formula 23]

[0089]

[Chemical formula 24]

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodisperse 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.

[0091]

[Chemical 25]

Then, 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 115. In addition, the third dye image stabilizer
Samples 116-124 were made without addition to the layers.

The thus-prepared sample was wedge-exposed with green light according to a conventional method, and then processed according to the following processing steps.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleach fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Dry 60-80 ° C 60 seconds The composition of each processing solution is as follows. Show.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of the} 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, the total volume is set to 1000 ml, and the pH of tank liquid is
Adjust the pH to 10.10 and the replenisher to pH 10.60.

Bleach-fixer (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 Water was added. Adjust the total volume to 1000 ml and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightening agent (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 each 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> represents the maximum absorption wavelength of the wedge at the reflection optical density of 1.0.

<Abs600> Absorbance of the wedge at 600 nm (the absorbance at λmax is 1.0
And)).

<Dmax> represents the maximum color density.

The results are shown in Table 3.

[0105]

[Table 3]

As is clear from Table 3, each sample using the magenta coupler of the present invention has a markedly reduced absorbance at 600 mm, and the maximum absorption wavelengths obtained from the comparative samples 102, 104 and 105 are color papers. Unsuitable for
The maximum absorption wavelength (λ mm) obtained from each sample using the coupler of the present invention is suitable for color paper and the color reproducibility is improved. Further, the maximum absorption wavelengths obtained from Comparative Samples 101, 103, 106 and 107 are suitable for color paper, but in the system in which the dye image stabilizer of the present invention is used in combination, the sample using the coupler of the present invention is more preferable. Good light resistance.

Example 2 Dye image stabilizer III- in the third layer of Sample 101 of Example 1
Samples 201 to 222 were prepared by replacing 8 with III-2 and IV-2 (each having a molar ratio to the coupler of 1). Sample 22 in which the dye image stabilizer was not added to the third layer
3 to 231 were prepared.

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

[0109]

[Table 4]

As is apparent from Table 4, it was found that the sample Nos. (208 to 222) of the present invention were superior in color reproducibility and light resistance to the comparative sample as in Example 1. Karu Further, it was found that a better effect can be obtained with respect to the light resistance than in Example 1.

Example 3 The dye image stabilizer III-8 in the third layer of Sample 101 of Example 1 was added.
Samples 301 to 323 were prepared by substituting two types of III-6 and IV-2 (each having a molar ratio to the coupler of 1), and the same evaluation as in Example 1 was performed using each sample. The results are shown in Table 5.

[0112]

[Table 5]

As is clear from Table 5, the examples of the present invention have the same effects as those of the example 1, and it is further found that the effects of light resistance are better than those of the example 2.

Example 4 The dye image stabilizer III-8 in the third layer of Sample 101 of Example 1 was added.
Samples 401 to 423 were prepared by substituting two kinds of III-10 and IV-2 (each having a molar ratio to the coupler of 1). The same evaluation as in Example 1 using each of the obtained samples was performed.

The results are shown in Table 6.

[0116]

[Table 6]

As is clear from Table 6, the same effects as in Example 1 were obtained in the present invention. Further, regarding the light resistance, a better effect was obtained as compared with Example 3.

As shown in the above results (Tables 3 to 6), the color reproducibility and color developability are all the same, but the light fastness is improved by using two kinds of dye image stabilizers in combination.
It has been found that a better result can be obtained in that effect.

[0119]

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 photographic light-sensitive material comprising at least one pyrazolotriazole magenta coupler represented by the following general formula [I] or general formula [II]. [Chemical 1] [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent an alkyl group, and X and Y correspond to a hydrogen atom or an oxidized product of a color developing agent. Represents a group capable of splitting off. 2. A silver halide emulsion layer containing a magenta coupler represented by the general formula [I] or the general formula [II] and at least a compound represented by the following general formula [III] or the general formula [IV]. The silver halide color photographic light-sensitive material according to claim 1, wherein one of them is contained. [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 Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring with a nitrogen atom. ]