JPH0736160A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain excellent color reproducibility and color developing property, and especially, to improve fastness against light of a magenta dye image by incorporating a specified magenta coupler. CONSTITUTION:This photosensitive material contains a magenta coupler expressed by formula I or formula II. In formulae I, II, R1 is a hydrogen atom or substituent and R2 is a hydrogen atom or substituent. Ar1, Ar2 are aryl groups and Ar1 and Ar2 may be same or different, and further, Ar1 and Ar2 may have substituents. X is a hydrogen atom or a group which can be released by the reaction with an oxidant of a developing agent. This pyrazoloazole magenta coupler is preferably used with an image stabilizer in one layer, however, the image stabilizer may be used in the layer adjacent to the layer containing this coupler. The compsn. of silver halide preferably used is silver chloride, silver chloride bromide, or silver chloride iodide bromide. This material can be preferably used for a color negative film, color paper, etc.

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 are obtained. Furthermore,
The present invention relates to a silver halide color photographic light-sensitive material capable of obtaining a dye image stable to 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 , 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-mentioned literature, the dye formed from the pyrazoloazole type magenta coupler has no side absorption. That this coupler is a good coupler, U.S. Pat.
No. 3,810,761 etc.

[0005]

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

[0006] Conventionally, research has been conducted to improve light fastness. For example, JP-A Nos. 59-125732 and 6
1-282845, 61-292639, and 61-279855 disclose a technique of using a pyrazoloazole-based magenta coupler in combination with a phenol compound or a phenyl ether compound.
61-72246, 62-208048, 62-157031, 63-163
No. 351 discloses a technique of using an amine compound in combination.

Further, JP-A-63-24256 proposes a pyrazoloazole-based magenta coupler having an alkyloxyphenyloxy group.

However, also in the above technique, the fastness to light of a magenta dye image is insufficient, and improvement thereof 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 to provide a silver halide color photographic light-sensitive material containing a magenta coupler represented by the following general formula [I] or general formula [II]. To be achieved.

[0011]

[Chemical 2]

[Wherein R ₁ represents a hydrogen atom or a substituent, R ₂ represents a hydrogen atom or a substituent, and Ar ₁ and Ar ₂
Represents an aryl group, Ar ₁ and Ar ₂ may be the same or different, Ar ₁ and Ar ₂ may further have a substituent, and X is a hydrogen atom or a color developing agent. It represents a group capable of splitting off upon reaction with an oxidant. First, the couplers represented by formulas [I] and [II] of the present invention will be described in more detail.

R ₁ represents a hydrogen atom or a substituent. These substituents are not particularly limited, but have 1 to
18 linear or branched alkyl groups (for example, methyl group, ethyl group, i-propyl group, t-butyl group, neopentyl group,
Pentadecyl group, etc.), cycloalkyl group having 3 to 10 carbon atoms (eg cyclopropyl group, cyclopentyl group, cyclohexyl group etc.), alkoxy group (eg methoxy group,
Ethoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkylthio group (eg methylthio group, dodecylthio group etc.), arylthio group (eg phenylthio group etc.) ), Acylamino group (eg, acetylamino group, benzoylamino group, etc.), ureido group (eg, phenylcarbamoylamino group, dimethylcarbamoylamino group, etc.), alkoxycarbonylamino group (eg, ethoxycarbonylamino group, etc.), aryloxycarbonylamino group (For example, phenoxycarbonylamino group and the like) and amino group (for example, dimethylamino group, anilino group and the like) are preferable. These groups may further have a substituent.

The substituent represented by R ₂ is not particularly limited, but is typically alkyl, aryl, alkenyl, cycloalkyl, cycloalkenyl, alkynyl,
Heterocycle, sulfonyl, hydroxy, carboxy, sulfinyl, phosphonyl, phosphinyl, acyl, carbamoyl, sulfamoyl, alkoxycarbonyl, aryloxycarbonyl groups, spiro compound residues, bridged hydrocarbon compound residues and the like can be mentioned.

The alkyl group represented by R ₂ preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group is preferably a phenyl group or a substituted phenyl group.

The alkenyl group represented by R ₂ 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. But it's okay. As a cycloalkenyl group,
Those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms are preferable.

The sulfonyl group represented by R ₂ 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 or an arylphosphonyl group. A phenyl group, an alkylphosphinyl group, an arylphosphinyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; Examples of the sulfamoyl group include an alkylsulfamoyl group, an arylsulfamoyl group, etc .;
5- to 7-membered ones are preferable, and specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like; spiro compound residues include spiro [3.3] heptane-1 -Yl etc .; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptane-1-yl, tricyclo [3.
3.1.1 ^3.7 ] Decan-1-yl, 7,7-dimethyl-bicyclo
[2.2.1] Heptan-1-yl and the like can be mentioned.

Each of the groups represented by R ₂ further includes those having a substituent.

Examples of the aryl group represented by Ar ₁ and Ar ₂ include a phenyl group, a 1-naphthyl group and a 9-anthranyl group. Of these, the most preferred is the phenyl group. The aryl group represented by Ar ₁ and Ar ₂ may further have a substituent, and the substituent is R
_The ones described in ₂ are mentioned. Ar ₁ and Ar ₂ may be the same or different, and Ar ₁ and Ar ₂
And may be linked by a linking group or a bond,
Ar ₁ or Ar ₂ and R ₂ may form a condensed ring.

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a color developing agent (leaving group). Examples of the leaving group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, a sulfonamide group, an acylamino group,

[0021]

[Chemical 3]

(Z is a carbon atom, an oxygen atom, a nitrogen atom,
It represents an atomic group selected from sulfur atoms and necessary for forming a 5- or 6-membered ring with a nitrogen atom. ) And the like.

Specific examples of the leaving group are shown below.

Halogen atom: atoms such as chlorine, bromine and fluorine Alkoxy group: ethoxy group, benzyloxy group, ethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4- Nitrophenoxy group, etc.Acyloxy group: Acetoxy group, myristoyloxy group, benzoyloxy group, etc.Arylthio group: Phenylthio group, 2-butoxy-5-octylphenylthio group, 2,5-Dihexyloxyphenylthio group, etc. Alkylthio group: Methylthio group , Octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, etc. Sulfonamide group: methanesulfonamide group, benzenesulfonamide group, etc. Acylamino group: heptafluorobutanamide group, pentachlorophenylcarbonylamino group, etc.

[0025]

[Chemical 4]

The following are examples of those represented by:

[0027]

[Chemical 5]

The leaving group is preferably a halogen atom, and most preferably a chlorine atom.

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

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

[Chemical 14]

[0039]

[Chemical 15]

Synthetic Example (Synthesis of M-22) Synthetic Route

[0041]

[Chemical 16]

Synthesis of Intermediate 3 To 15.0 g (52 mmol) of triphenylacetic acid, 150 ml of toluene and 7.5 ml of thionyl chloride were added, and the mixture was heated under reflux for 7 hours. After completion of the reaction, excess thionyl chloride and the solvent toluene were distilled off under reduced pressure to obtain 16.1 g of Intermediate 1.

Intermediate product 2 1 was added to 16.1 g of the obtained intermediate product 1.
After 0.5 g (47 mmol) and 200 ml of acetonitrile were added and heated under reflux for 3 hours, the solvent acetonitrile was distilled off under reduced pressure. Furthermore, 300 ml of toluene and 5.0 g of p-toluenesulfonic acid
After heating and refluxing for 3 hours, add about 200 m of toluene under normal pressure.
l Distilled off. After 300 ml of ethyl acetate was added to the obtained reaction solution, insoluble materials were removed by filtration under reduced pressure, and the reaction solution was washed with an aqueous solution of sodium hydrogen carbonate until the liquid became neutral. The obtained organic phase was dried over anhydrous sodium sulfate, and then dissolved to be distilled off under reduced pressure to obtain a brown oily substance. Then, this was purified by silica gel column chromatography to obtain 15.3 g (34.9 mmol) of light brown amorphous intermediate 3.

(Structure was identified by ¹ H NMR, IR, FD mass spectrum.) Synthesis of Intermediate 4 To 15.3 g (34.9 mmol) of Intermediate 3 was added 120 ml of acetic anhydride, and the mixture was heated under reflux for 4 hours, About 100 ml of acetic acid produced by the reaction with acetic anhydride was distilled off under pressure. The reaction mixture was ice-cooled, methanol (40 ml) and concentrated hydrochloric acid (15 ml) were added dropwise, and the mixture was heated under reflux for 4 hr. The reaction solution was cooled to room temperature, the precipitated sulfur was filtered off, and then methanol was removed under reduced pressure.
Neutralized with sodium hydroxide. 300 ml of ethyl acetate here
Was added for extraction, the obtained organic phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was then recrystallized from acetonitrile to give a pale yellow crystalline intermediate 4 1
0.9 g (26.9 mmol) was obtained.

(Structure was identified by ¹ H NMR, IR, FD mass spectrum.) Synthesis of M-22 10.9 g (26.9 mmol) of Intermediate 4 was dissolved in 50 ml of chloroform and cooled with ice to a liquid temperature of 5. At a temperature of ℃, N-chlorosuccinimide 3.6 g (26.9 mmol) was added little by little as a solid. After stirring at 5 ° C for 2 hours, the reaction solution was added to 100 m.
After washing twice with 1 L of water and further drying over anhydrous magnesium sulfate, the solvent chloroform was distilled off under reduced pressure. The obtained product was recrystallized from acetonitrile to obtain 8.1 g (18.4 mmol) of white crystals of M-22.

(The structure was fixed by ¹ H NMR, IR and FD mass spectra.) The coupler of the present invention is usually 1 × 10 6 per 1 mol of silver halide.
It can be used in the range of ^-3 to 1 mol, preferably 1 x 10 ^-2 to 8 x 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 on pages 133 to 137 of JP-A No. 62-215272. -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 61-1
Exemplified Compound PH-1 to 45552 No. 8 to 10
PH-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 I
II-14, IV-1 to IV-24, V-13 to V-17, and 3-39956
No. 10 to 11 exemplified compounds II-1 to II-33,
Compound B-1 described on pages 8 to 11 of JP-A-2-167543
To B-65, exemplified compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439, and the like.

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 mol% based on the pyrazoloazole type magenta coupler of the present invention. It is 250 mol.

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

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

The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide, silver iodochloride,
Any of silver chlorobromide, silver chloroiodobromide, silver chloride, and the like used in ordinary silver halide emulsions 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 particles, any ratio of (100) plane to (111) plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

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

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

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

A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye 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. Among these, benzoyl acetanilide compounds and pivaloyl acetanilide compounds can be advantageously used.

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

Between the emulsion layers of the light-sensitive material (the same color-sensitive 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 which can be preferably used are those described in Research Disclosure 17643, Item VII J.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material contain an ultraviolet ray inhibitor in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like and to prevent deterioration of 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.

[0067]

EXAMPLES Next, the present invention will be explained based on examples.
Embodiments of the present invention are not limited to these.

Example 1-1 On a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side, each layer having the constitution shown in Tables 1 and 2 below contains titanium oxide. It was coated on the side of the polyethylene layer to be used to prepare a multilayer silver halide color photographic light-sensitive material sample 101. 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 contained 7 ml of 20% aqueous solution of surfactant (SU-2). Then, 220 ml of 10% aqueous gelatin solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver chlorobromide 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 second to seventh layer coating solutions were prepared in the same manner as the first layer coating solution. 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.

[0072]

[Table 1]

[0073]

[Table 2]

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

[0075]

[Chemical 17]

[0076]

[Chemical 18]

[0077]

[Chemical 19]

[0078]

[Chemical 20]

[0079]

[Chemical 21]

[0080]

[Chemical formula 22]

Blue-sensitive silver chlorobromide emulsion (Em-B) Monodisperse cubic emulsion having an average particle size of 0.85 μm, a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer 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 chlorobromide emulsion (Em-G) Monodisperse cubic 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 chloroauric acid 1.0 mg / mol AgX stable Agent STAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX Red-sensitive silver chlorobromide emulsion (Em-R) Average particle size 0.50 μm, coefficient of variation = 0.08 Cubic emulsion with 99.5 mol% silver chloride content Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB 1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX variation coefficient is calculated by the following equation 1.

[0082]

[Equation 1]

Here, ri represents the particle size of each particle, and ni represents the number thereof. The grain size means the diameter of a spherical silver halide grain, and the diameter of a cubic image or a grain having a shape other than spherical when the projected image is converted into a circular image having the same area.

The structural formulas of the compounds used in each monodisperse cubic emulsion are shown below.

[0085]

[Chemical formula 23]

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 107.

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

Processing 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 liquid 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 800ml 800ml 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'-diaminostilbene sulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, the total volume is set to 1 liter and p
Adjust H = 10.10 and pH in replenisher to 10.60.

Bleach-fix 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 Water is added. Bring the total volume to 1 liter 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 brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Add water to bring the total volume to 1 liter and adjust the pH with sulfuric acid or potassium hydroxide. Adjust to 7.0.

The following evaluation was carried out using the sample after the development processing. The results are shown in Table 3.

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

Dmax; represents the maximum color density.

[0096]

[Table 3]

As is clear from Table 3, Samples 102 to 113 using the magenta coupler of the present invention are superior in color development and light resistance to Comparative Sample 101.

Example 1-2 Sample 10 in which the magenta coupler of the third layer of Sample No. 101 of Example 1-1 was replaced with an equimolar coupler shown in Table 4 below.
8 to 112 created.

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

[0100]

[Table 4]

As is clear from Table 4, the samples 109 to 112 using the magenta coupler of the present invention are superior to the comparative sample 108 in both color development and light resistance.

Example 1-3 Sample 113 in which the magenta coupler of the third layer of Sample 101 of Example 1-1 was replaced with an equimolar coupler shown in Table 5 below.
Created ~ 117.

The same evaluation as in Example 1-1 was performed using the obtained sample. The results are shown in Table 5.

[0104]

[Table 5]

As is clear from Table 5, Samples 114 to 117 using the magenta coupler of the present invention are superior to Comparative Sample 113 in both color development and light resistance.

Example 1-4 The reflection spectral absorption spectra of Samples 101 to 113 of Example 1-1 were measured, and the spectral absorption characteristics λmax and Abs600 were evaluated.
The results are shown in Table 6.

Λmax; represents the maximum absorption wavelength of the wedge at a reflection optical density of 1.0.

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

[0109]

[Table 6]

As is clear from Table 6, in Samples 102 to 107 using the magenta coupler of the present invention, the absorbance at 600 nm is reduced (absorption becomes sharper) as compared with Sample 101 using the comparative coupler. Reproducibility is improved.

Example 2 One side (surface) of triacetyl cellulose film support
Was subjected to a subbing process, and then, with the support sandwiched, layers having the compositions shown below were sequentially formed on the surface (back surface) opposite to the surface subjected to the subbing process from the support side. The addition amount in the silver halide photographic light-sensitive material is the amount per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Backside first layer Aluminasol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Backside second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg A multilayer color photographic light-sensitive material sample 201 was prepared by sequentially forming each layer having the composition shown below from the support side on the surface of an acetyl cellulose film support.

First layer; antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-4) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling point solvent (DOP) 0.20 g High boiling point solvent ( TCP) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm) (average) Iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.3 g Sensitizing dye (RS-2) 3.2 × 10 ⁻⁴ (mol / silver 1) Sensitizing dye (RS-3) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (RS-4) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (EC-3) 0.50 g Cyan coupler (EC-4) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (DOP) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) ( Average iodine content 7.5 mol%) 0.9 g Sensitizing dye (RS-2) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (RS-3) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (RS-4) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (EC-4) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point Solvent (DOP) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size 0.3 μm) (Average iodine content 2.0 mol%) 0.2 g Sensitizing dye (GS 2) 6.7 × 10 ^-4 (mol / mole of silver) Sensitizing dye (GS-3) 0.8 × 10 -4 ( mol / mole of silver) Magenta coupler (EM-4) 0.45 g Colored magenta coupler (CM-1 ) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (TCP) 0.7 g Gelatin 1.0 g Seventh layer; high sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) (Average iodine content 7.5 mol%) 0.9 g Sensitizing dye (GS-4) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (GS-5) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) ) Sensitizing dye (GS-6) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (EM-4) 0.35 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High Boiling point solvent (TCP) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (TCP) 0.15 g Gelatin 1.0 g 9th layer; low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm) (average iodine content 8.0 mol%) 0.25 g Sensitizing dye ( BS-3) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (EY-2) 0.6 g Yellow coupler (EY-3) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (TCP) 0.18 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 μm) (average iodine content 8.5 mol%) 0.5 g Sensitizing dye (BS-4) 3 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (BS-5) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (EY-2) 0.18 g Yellow coupler (EY-3) 0.10 g High boiling point solvent (TCP) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size) 0.08μm) 0.3g Ultraviolet absorber (UV-4) 0.07g Ultraviolet absorber (UV-5) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling point solvent (DOP) 0.07 g High boiling point solvent (DBP) 0.07 g Gelatin 0.8 g 12th layer; Second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl meta Acrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size 3 μm) 0.13 g Incidentally, the above-mentioned photosensitive material sample 201 is a compound SU-
1, SU-4, viscosity modifier, hardener HH-2, HH-
3, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and DI-1 (9.4 g / m
² ) is included.

The silver iodobromide emulsion of the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

The solution <G-1> was heated at a temperature of 70 ° C., pAg7.8 and pH.
Keeping at 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, the flow rate is gradually increased while maintaining the flow rate ratio of <H-1> and <S-1> of 1: 1 (at the end of the process). The flow rate was 3.6 times the initial flow rate) and was added over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg10.1 and pH6.0.
-2> was added at a flow rate ratio of 1: 1 by gradually increasing the flow rate (the flow rate at the end was 5.2 times the initial flow rate) for 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a grain size distribution of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> 100.0 g of ossein gelatin 10% by weight solution of compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% ammonia solution Equivalent Finish with water 1030.5ml <H-2> Ocein gelatin 302.1g Potassium bromide 770.0g Iodine Potassium iodide 33.2g Finish with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% aqueous ammonia solution Equivalent Finish with water 3776.8ml Average particle size of seed crystal, temperature, pAg, pH, flow rate, addition time and The above emulsions having different average grain sizes and different silver iodide contents were prepared by changing the halide composition. All were core / shell type monodisperse emulsions having a variation coefficient of particle size distribution of 20% or less.

Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6-methyl-1,3,3.
Add a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole.

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

[0124]

[Chemical formula 24]

[0125]

[Chemical 25]

[0126]

[Chemical formula 26]

[0127]

[Chemical 27]

[0128]

[Chemical 28]

[0129]

[Chemical 29]

[0130]

[Chemical 30]

[0131]

[Chemical 31]

Samples 202 to 219 were prepared in the same manner as in Sample 201, except that the magenta couplers in the sixth and seventh layers of Sample 201 were changed to equimolar magenta couplers shown in Table 8.
The light-sensitive materials 201 to 219 created as described above are exposed to white light through a step wedge for sensitometry,
It processed according to the following development processing [I].

Development Processing [I]

[0134]

[Table 7]

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter and add potassium hydroxide or 20
Adjust to pH 10.06 with% sulfuric acid.

Color developing replenisher water 800 ml potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.18 with% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was used. Adjust to pH 4.4.

Bleaching Replenisher Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.0 with aqueous ammonia or glacial acetic acid ，
Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting to pH 6.2 with aqueous ammonia or glacial acetic acid,
Add water to make 1 liter.

Fixing replenisher liquid 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid,
Add water to make 1 liter.

Stabilizer and stable replenisher Water 900 ml Paraoctylphenol ethylene oxide 10 mol Addition product 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml Add water to make 1 liter and use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

Further, the samples 201 to 219 were subjected to the development processing (development processing [II]) in the same manner as the development processing [I] except that the pH of the color developing solution of the development processing [I] was changed to 9.90.

For each of the developed samples, the maximum density of magenta color development was measured by green light using an optical densitometer PDA-65 (manufactured by Konica Corporation). Maximum color density,
Table 8 shows the specific sensitivity and pH variability.

The pH variability was calculated by the following equation.

[0146]

[Equation 2]

[0147]

[Table 8]

The specific sensitivities in Table 8 are the relative values of the reciprocal of the exposure amount that gives the fog density + 0.10 density, and are shown by the value when the sample 201 is 100. Further, the specific sensitivity and the maximum density are the development processing [I]
Is the measured value in.

As is clear from Table 8, Samples 202 to 210 using the magenta coupler of the present invention are remarkably excellent in maximum density, sensitivity and pH variability as compared with Comparative Sample 201 using a known coupler.

[0150]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention is excellent in image storability, color developability and color reproducibility, and exhibits color developability in response to changes in the conditions of color developing solutions, especially variations in pH value. It has an excellent effect that the fluctuation is small.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising a magenta coupler represented by the following general formula [I] or general formula [II]. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom or a substituent, R ₂ represents a hydrogen atom or a substituent, Ar ₁ and Ar ₂ represent an aryl group, and Ar ₁ and Ar ₂ may be the same or different. May be
Further, Ar ₁ and Ar ₂ may have a substituent, and X 1
Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]