JPH0829931A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic material containing a cyano-compound coupler which has high resistance to darkening and discoloring of an formed color image and to light rays by containing a specified cyano-compound coupler. CONSTITUTION:A silver halide color photographic material contains a cyano- compound coupler having a formula I or a formula II. Or the material contains at least one of cyano-compound couplers having the formula I or the formula II and at least one of cyano-compound couplers having a formula III while these compounds being combined. In the formula I, R<1>-R<3> and R<4> stand respectively for a substituted or unsubstituted alkyl group and three of the R<1>, R<2>, and R<3> or two of them may bond and form a ring. In the formula II, R<5> stands for an unsubstituted alkyl group, R<6> stands for hydrogen atom, a C<1-10> branching or straight chain alkyl group, n stands for 1-5 integer, and R<1>-R<3> are the same in the formula I. In the formula III, R<7> stands for a substituted or unsubstituted alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a dye image containing a cyan coupler excellent in solubility and dispersion stability and having good color reproducibility and storage stability can be obtained. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In order to form a dye image using a silver halide color photographic light-sensitive material, an aromatic primary amine type color developing agent is usually used as a halogen in the exposed silver halide color photographic light-sensitive material. When the silver halide grains are reduced, they are oxidized themselves, and this oxidant reacts with a coupler previously contained in the silver halide color photographic light-sensitive material to form a dye. Usually, as the coupler, three types of couplers that form three dyes of yellow, magenta and cyan are used in order to perform color reproduction by the subtractive color method.

Each coupler is usually dissolved in a water-insoluble high-boiling point organic solvent or a solvent in which a co-solvent is optionally used in combination with this solvent and added to the silver halide emulsion.

[0004]

Known cyan couplers include 2-acylamino-5-ethylphenol cyan couplers in which the 2-position of phenol is substituted with an acylamino group, and 2- and 5-positions of phenol. 2,5-diacylaminophenol cyan couplers substituted with an acylamino group can be mentioned. However, the dye image formed is insufficient in terms of dark fading in the former and light fastness in the latter, so that further improvement is required.

Accordingly, it is an object of the present invention to provide a silver halide color light-sensitive material characterized by containing a cyan coupler excellent in dark fading and light fastness of a dye image formed.

[0006]

The above object of the present invention can be achieved by the following constitutions.

(1) A silver halide color light-sensitive material containing a cyan coupler represented by the above general formula [I] (Chemical formula 1).

(2) A silver halide color light-sensitive material containing a cyan coupler represented by the general formula [II] (formula 2).

(3) At least one of the cyan couplers represented by the general formula [I] (formula 1) and the cyan coupler represented by the general formula [III] (formula 3) on the support. A silver halide photographic light-sensitive material containing at least one in combination.

(4) At least one of the cyan couplers represented by the above general formula [II] (Chemical formula 2) on the support and the cyan coupler represented by the above general formula [III] (Chemical formula 3) A silver halide photographic light-sensitive material containing at least one in combination.

(5) At least one of the cyan couplers represented by the general formula [I] (Formula 1) and the cyan coupler represented by the general formula [IV] (Formula 4) on the support. A silver halide photographic light-sensitive material containing at least one in combination.

(6) At least one of the cyan couplers represented by the general formula [II] (formula 2) and the cyan coupler represented by the general formula [IV] (formula 4) on the support. A silver halide photographic light-sensitive material containing at least one in combination.

The present invention will be specifically described below.

First, the above-mentioned general formula [I] of the present invention (Formula 1)
The cyan coupler represented by will be described.

[0015]

Embedded image

In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a substituted or unsubstituted alkyl group. Further, three groups of R ¹ , R ² and R ³ or two groups thereof may be bonded to each other to form a ring.

In the present invention, the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ in the above general formula [I] is linear or branched, for example, methyl group, ethyl group, propyl group. Group, butyl group, octyl group and the like. The groups represented by R ¹ , R ² , R ³ and R ⁴ may have a single or a plurality of substituents, and typical examples of the substituent include a halogen atom (eg, a fluorine atom, Chlorine atom, bromine atom, etc.), hydroxyl group, cyano group, nitro group, alkoxy group (eg methoxy group, ethoxy group etc.), aryloxy group (eg phenoxy group etc.), alkyl sulfonamide group (eg methyl sulfonamide group, Octyl sulfonamide group etc.), aryl sulfonamide group (eg phenyl sulfonamide group, naphthyl sulfonamide group etc.), alkylsulfamoyl group (eg butylsulfamoyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group) Moyl group etc.), alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryl Luoxycarbonyl group (eg, phenyloxycarbonyl group, etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, alkoxy group,
Examples thereof include a carboxyl group, an alkylcarbonyl group, an arylcarbonyl acid and an aminocarbonyl group.

Of the above groups, R ¹ , R ² and R ³
The substituent represented by is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group in terms of dark fading and light resistance. Further, the substituent of the substituted alkyl group represented by R ⁴ is preferably a phenoxy group from the viewpoint of color reproducibility. Among the general formulas [I], the cyan coupler represented by the general formula [II] is more preferable.

[0019]

[Chemical 6]

In the formula, R ⁵ represents an unsubstituted alkyl group,
R ⁶ represents a hydrogen atom or a branched or straight chain alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5. R ¹ , R ² and R ³ are R ¹ , R ² in the general formula [I].
And R ³ are synonymous with each other.

Examples of the alkyl group represented by R ⁵ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a t-amyl group, an octyl group and a pentadecyl group. The alkyl group represented by R ⁶ is, for example, a methyl group, an ethyl group, an isopropyl group, a butyl group, a hexyl group or a decyl group.

Typical examples of the cyan coupler of the present invention represented by the general formulas [I] and [II] are shown below.
The present invention is not limited to these.

[0023]

[Chemical 7]

[0024]

Embedded image

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[Synthesis Example] Exemplified Compounds [I] -4 and [I
I] -5 was synthesized by the following route.

[0029]

[Chemical 12]

(Synthesis of Intermediate (1)) 25.0 g of Intermediate (1)
10.1 g of pivalic acid chloride (0.13 mol),
And refluxed with ethyl acetate (250 ml) for 5 hours. After the reaction was completed, the reaction solution was cooled with ice and the precipitate was filtered to obtain the intermediate (2).
2.95 g was obtained (yield 82%).

(Synthesis of Intermediate (3)) 8.00 g of Intermediate (2)
Dissolve (29 mmol) in 200 ml of ethanol and add 5.0 ml of concentrated hydrochloric acid.
(60 mmol), 0.8% of 5% palladium-carbon was added and hydrogenated. After the reaction was completed, the mixture was filtered using diatomaceous earth, and the filtrate was subjected to solvent removal under reduced pressure. The obtained residue was recrystallized from acetonitrile to obtain 6.73 g of the intermediate (3) (yield 82%).

(Synthesis of Exemplified Compound [I] -4) Intermediate
(3) 1.00 g (3.6 mmol) in 10 ml of ethyl acetate as an intermediate
(4) 1.14 g (4.0 mmol), N, N-dimethylaniline 1.14 ml
The mixture was heated under reflux with (9.0 mmol) for 1 hour. After cooling, the reaction solution was washed with hydrochloric acid water and water in this order and dried. After distilling off the solvent under reduced pressure, it was recrystallized from acetonitrile to give the exemplified compound [I] -4.
Was obtained (melting point: 105.5-106.0 ° C, yield: 82%).

(Synthesis of Exemplified Compound [II] -5) Intermediate
(4) 6.7 g (24 mmol) of ethyl acetate 70 ml, intermediate (5) 9.3
g (26 mmol), N, N-dimethylaniline 7.6 ml (60 mmol)
The mixture was heated under reflux for 2 hours. After completion of the reaction, the mixture was allowed to cool, and the reaction solution was washed with hydrochloric acid water and water in this order. After drying, the solvent was distilled off under reduced pressure, and the obtained residue was recrystallized from methanol to obtain 11.5 g of Exemplified Compound [II] -5 (melting point 189 to 190 ° C., yield 85
%).

The structure was confirmed by ¹ H-NMR, IR and MASS spectra.

Further, these cyan couplers can be used in combination with conventionally known cyan couplers. In the silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on the support, the present inventors have added the above-mentioned general formula [I] or the above general formula in the silver halide emulsion layer. At least one of the cyan couplers represented by the formula [II] and the general formula [III]
It has been found that, by incorporating at least one of the cyan couplers represented by the above formula, not only the dark fading property and the light resistance but also the color reproducibility and the color developability are improved.

The cyan coupler represented by the general formula [III] will be described below.

[0037]

[Chemical 13]

In the formula, R ⁷ represents a substituted or unsubstituted alkyl group. The unsubstituted alkyl group is, for example, an octyl group or a dodecyl group. R ⁷ may have a single or a plurality of substituents, and typical examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, a carboxyl group,
Alkyl group (eg, methyl group, ethyl group, propyl group,
Butyl group, octyl group, dodecyl group, etc.), aralkyl group, cyano group, nitro group, alkoxy group (eg methoxy group, ethoxy group), aryloxy group, alkyl sulfonamide group (eg methyl sulfonamide group, octyl sulfonamide group) Etc.), aryl sulfonamide group (eg phenyl sulfonamide group, naphthyl sulfonamide group etc.), alkylsulfamoyl group (eg butylsulfamoyl group etc.), arylsulfamoyl group (eg phenylsulfamoyl group etc.) , Alkyloxycarbonyl group (eg methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), aminosulfonamide group (eg dimethylaminosulfonamide group), alkylsulfonyl group, arylsulfonyl , Alkylcarbonyl group, arylcarbonyl group, aminocarbonyl amido group, a carbamoyl group, and the like sulfinyl group. Two or more kinds of these substituents may be introduced.

In the present invention, the cyan coupler represented by the above general formula [III] is more preferably the one represented by the following general formula [IV] from the viewpoint of color reproducibility.

[0040]

Embedded image

In the formula, R ⁸ is an unsubstituted alkyl group (eg, methyl group, ethyl group, isopropyl group, t-butyl group, t-butyl group,
Amyl group, octyl group, dodecyl group, etc.). More preferably, it is a t-butyl group, a t-amyl group or an octyl group. R ⁹ is, for example, a hydrogen atom or a branched or straight chain alkyl group having 1 to 10 carbon atoms. n has the same meaning as n in the general formula [II].

Typical examples of the cyan coupler represented by the general formula [III] or [IV] are shown below, but the present invention is not limited thereto.

[0043]

[Chemical 15]

[0044]

Embedded image

[0045]

[Chemical 17]

[0046]

Embedded image

These compounds can be easily synthesized by referring to the method of Japanese Patent Publication No. 3-71700.

When the cyan coupler of the present invention represented by the general formula [I] or [II] and the cyan coupler of the present invention represented by the general formula [III] or [IV] are used in combination. , The general formula [I] or [I
At least one of the cyan couplers represented by the formula [I] and at least one of the cyan couplers represented by the general formula [III] or [IV] can be used in an optional combination in an arbitrary blending amount. However, it is preferable that the cyan coupler represented by the general formula [I] or [II] is contained in an amount of 10 to 50 mol% based on the total amount of these cyan couplers, and more preferably 10 to 30 mol%. is there.

The silver halide color photographic light-sensitive material of the present invention may be any one provided that at least one silver halide emulsion layer is provided on a support, and a typical example thereof is color. Negative and positive films, color photographic papers, color slides, or special photosensitive materials for printing, X-rays, high resolution, etc.
It is particularly suitable as a color photographic paper.

The light-sensitive material using the coupler of the present invention, such as this color photographic paper, may be monochromatic or polychromatic. In the multi-color light-sensitive material, the coupler of the present invention may be contained in any layer, but it is usually contained in the red light-sensitive silver halide. The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of the three primary color regions of the spectrum. Each building block can consist of a single layer or multiple emulsion layers sensitive to certain regions of the spectrum. The constituent layers of the light-sensitive material, including the layers of the image-forming constituent units, can be arranged in various orders as known in the art.

A typical multicolor photosensitive material is at least 1
Cyan dye image-forming structural unit (at least one of the cyan couplers is a coupler of the present invention) consisting of at least one red-sensitive silver halide emulsion layer containing two cyan couplers, and at least one magenta coupler. A magenta dye image-forming structural unit comprising at least one green-sensitive silver halide emulsion layer, at least 1
It comprises a yellow dye image-forming structural unit comprised of at least one blue-sensitive silver halide emulsion layer containing one yellow coupler supported on a support.

The light-sensitive material can have additional layers such as filter layers, intermediate layers, protective layers, subbing layers and the like.

In order to incorporate the coupler of the present invention into an emulsion, a conventionally known method may be used. For example, tricresyl phosphate, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate or a low boiling point solvent such as butyl acetate or butyl propionate, alone or as necessary in a mixed solution thereof, the coupler of the present invention. Is dissolved alone or in combination, then mixed with an aqueous gelatin solution containing a surfactant, then emulsified with a high-speed rotating mixer or colloid mill, and then added to silver halide to be used in the present invention. Emulsions can be prepared.

The silver halide composition preferably used in the light-sensitive material using the coupler of 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. That is,
When the silver halide emulsion is used for color photographic paper, particularly rapid developing property is required. Therefore, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and a chloride containing at least 1% of silver chloride. Particularly preferred is silver, silver chlorobromide or silver chloroiodobromide.

The silver halide emulsion is chemically sensitized by a conventional method. Further, it can be optically sensitized to a desired wavelength range.

The silver halide emulsion contains an antifoggant or stabilizer in the photographic industry for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage, or during photographic processing, and / or keeping the photographic performance stable. Compounds known as can be added.

The color light-sensitive material using the coupler of the present invention includes a color fog-preventing agent, a dye image stabilizer, an anti-UV agent, an antistatic agent, a matting agent, which are usually used in light-sensitive materials.
A surfactant or the like can be used.

Regarding these, for example, Research Disclosure Vol. 176, 22-31
The description on page (December 1978) can be referred to.

The color photographic light-sensitive material using the coupler of the present invention can form an image by performing color development processing known in the art.

The color photographic light-sensitive material using the coupler according to the present invention may contain a color-developing agent as the color-developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and may be processed with an alkaline activating bath. it can.

The color photographic light-sensitive material using the coupler of the present invention is subjected to bleaching treatment and fixing treatment after color development.
The bleaching process may be performed simultaneously with the fixing process.

After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0063]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 A red light-sensitive color light-sensitive material sample 1 was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side. Unless otherwise specified, the addition amount of the compound is per 1 m ² (silver halide is a silver conversion value).

First Layer: Emulsion Layer Red consisting of 1.3 g of gelatin, 0.21 of red-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) and comparative cyan coupler a 9.1 × 10 ^-4 mol dissolved in 0.45 g of dioctyl phosphate. Sensitive emulsion layer.

Second layer: protective layer A protective layer containing 0.50 g of gelatin. As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added to 0.017 g per 1 g of gelatin.

Next, in the same manner as in the sample 2 of the present invention, the comparative coupler a in the sample 1 was replaced by the coupler shown in Table 1 (the addition amount was the same molar amount as the comparative coupler a).
~ 7 were produced.

The samples 1 to 7 obtained above were each subjected to wedge exposure according to a conventional method, and then developed in the next step.

The processing conditions are as follows.

Treatment process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-40 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Color developer Pure water 800ml Triethanolamine 10g N, N-Diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0 g Diethylene glycol 10g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g Potassium carbonate 27g Water Is added to adjust the total amount to 1 l, and the pH is adjusted to 10.10.

Bleach-fixing solution 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 to bring the total volume to 1 liter and add potassium carbonate or Adjust pH = 5.7 with glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-dihydroxyethylidene-1,1-diphosphonic acid 2.0 g o-Phenylphenol sodium 1.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to make the total volume 1 l, Adjust to pH = 7.0 with sulfuric acid or potassium hydroxide.

The concentrations of the samples 1 to 7 treated as described above were measured using a densitometer (KD-7 type manufactured by Konica Corporation), and the treated samples were treated at high temperature and high humidity (60 ° C, 80
% RH), the dye image was examined for heat resistance and humidity resistance (that is, dark fading) by allowing it to stand for 14 days.

After irradiating each sample with a xenon fade meter for 10 days, the concentration was measured and the light resistance was examined. The results are shown in Table 1. However, the heat resistance / moisture resistance and light resistance of the dye image are expressed by the percentage of dye remaining after the heat / moisture resistance and light resistance test for the initial density of 1.0.

[0075]

[Chemical 19]

[0076]

[Table 1]

As is clear from the results shown in Table 1, the samples using the cyan coupler of the present invention had a higher dye residual rate than the comparative sample using the comparative coupler C-1 and had a dark fading (heat resistance) property.・ It can be seen that it has excellent moisture resistance) and light resistance, and is robust. Further, it is found that the sample is superior in dark fading and robust as compared with Comparative sample 2 using [IV] -2 (only).

Example 2 In the sample of Example 1, the comparative coupler C-1 is shown in Table 2 (the addition amount is the same molar amount as the comparative coupler C-1, and in the case of two couplers, the coupler a is the comparative coupler C).
1/5 molar amount of -1, coupler b is 4 of comparative coupler C-1
Samples 8 to 18 of the present invention were prepared in exactly the same manner except that the amount was changed to / 5 mol amount).

Samples 8 to 18 exposed and processed in the same manner as in Example 1 were measured by a densitometer (KD manufactured by Konica Corporation).
-7 type) was used to measure the density, and the color reproducibility of the dye image was visually evaluated (5 levels). Further, heat resistance, humidity resistance and light resistance were tested in the same manner as in Example 1. Table 2 shows the results.

[0080]

[Table 2]

As is clear from the results shown in Table 2, the sample using the cyan coupler of the present invention was C-1 as in Example 1.
Alternatively, not only are they stronger than Comparative Samples 8 and 10 using [IV] -2 (only), but also use a cyan coupler represented by the above general formula [III] or [IV] in combination. Thus, a color forming dye image having good color reproducibility is formed. In particular, when the coupler represented by the general formula [IV] is used in combination, the effect of improving the color reproduction is obtained by comparing with the comparative coupler C-1.
And a coupler represented by the general formula [IV] are used together. This is because the use of the cyan coupler of the general formula [III] or [IV] in combination provided a completely unexpected synergistic effect. In addition, the formed dye image exhibits extremely satisfactory properties in terms of light resistance, heat resistance and humidity resistance.

Example 3 A polyethylene support containing polyethylene oxide was laminated on one side of a paper support and a polyethylene support containing titanium oxide was laminated on the other side of the support. Sample No. 19 was prepared by coating on the side of the. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.67 g, additive (HQ-1) 0.67 g, a 60 ml of ethyl acetate was added to 6.67 g of the anti-radiation dye (AI-3) and the high boiling point organic solvent (DNP) and dissolved, and this solution contained 7.0 ml of 20% surfactant (SU-1) 1
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer.
This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions 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. In addition, (H-1) was added to the second and fourth layers and (H-2) was added to the seventh layer as a hardening agent. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount added to the silver halide photographic material is expressed in grams per m ² unless otherwise specified.

The layer structure is as shown in the table below.

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

Embedded image

[0088]

[Chemical 21]

[0089]

[Chemical formula 22]

[0090]

[Chemical formula 23]

[0091]

[Chemical formula 24]

[0092]

[Chemical 25]

(Preparation of blue-sensitive silver halide emulsion) In 1000 ml of a 2% gelatin aqueous solution kept at 40 ° C., the following (solution A) and (solution B) were taken for 30 minutes while controlling pAg = 6.5 and pH = 3.0. At the same time, and then add the following (C solution) and (D solution)
Simultaneously added over 180 minutes while controlling Ag = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For the control of pAg, a control solution having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution consisting of sodium chloride and potassium bromide, the ratio of chloride ion and bromide ion is 99.8: 0.2, and the concentration of the control solution is mixture of solution A and solution B. 0.1 mol / l, C
When the liquid and the liquid D were mixed, the amount was 1 mol / l.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

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 Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as EMP-1, except that the average particle size is 0.43 μm.
A monodisperse cubic emulsion EMP-2 having m, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizing agent STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX ( Method for preparing red-sensitive silver halide emulsion) (solution A) and (B)
The average particle size is 0.50 μm in the same manner as EMP-1 except that the addition time of (solution) and the addition time of (solution C) and (solution D) are changed.
A monodisperse cubic emulsion EMP-3 having m, coefficient of variation (S / R) = 0.08, and silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizing agent STAB-16 x10 ^-4 mol / mol AgX sensitizing dye RS-11 x10 ^-4 mol / mol AgX fluctuation The coefficient is calculated from the standard deviation (S) and the average particle size (R), and S = [Σ (R _i −R) ² / Σn _i ] ^1/2 R _i represents the particle size, and n _i is the particle size. Represents the number of particles with R _i .

[0101]

[Chemical formula 26]

[0102]

[Chemical 27]

Next, in Sample 19, the cyan coupler (C-1) of the fifth layer is shown in Table 3 (the addition amount is C-
Samples 20 to 30 of the present invention were prepared in exactly the same manner except that the same molar amount as 1 was used, and the amount was changed to that shown in Table 3.

The samples 19 to 30 obtained above were each subjected to wedge exposure by red light according to a conventional method, and then processed in the same processing steps as in Example 1. After that, a densitometer (Konica K
D-7) was used to measure the density, and the color reproducibility of the dye image was visually evaluated. Further, the light resistance and heat / moisture resistance tests were conducted in the same manner as in Example 1. The results are also shown in Table 5.

[0105]

[Table 5]

As is clear from the results of Table 5, when the cyan coupler of the present invention is used as in the present invention, the color reproducibility is good and the heat resistance and heat resistance of the multilayer silver halide color photographic light-sensitive material are good. A dye image is formed which is highly satisfactory in moisture resistance and light fastness.

[0107]

According to the present invention, there can be provided a silver halide color light-sensitive material characterized by containing a cyan coupler excellent in dark fading and light fastness of a dye image formed by the present invention.

Claims (6)

[Claims] 1. A silver halide color light-sensitive material containing a cyan coupler represented by the following general formula [I]. Embedded image [In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a substituted or unsubstituted alkyl group. Also, R ¹ , R ² and R ³
The above three groups or two groups thereof may be bonded to each other to form a ring. ] 2. A silver halide color light-sensitive material containing a cyan coupler represented by the following general formula [II]. Embedded image [In the formula, R ⁵ represents an unsubstituted alkyl group, R ⁶ represents a hydrogen atom or a branched or linear alkyl group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5. Also, R ¹ ,
R ² and R ³ are R ¹ , R ² and R ³ in the general formula [I].
And are synonymous with each other. 3. At least one of the cyan couplers represented by the general formula [I] and at least one of the cyan couplers represented by the following general formula [III] on a support.
A silver halide photographic light-sensitive material characterized by containing two in combination. Embedded image [In the formula, R ⁷ represents a substituted or unsubstituted alkyl group. ] 4. At least one of the cyan couplers represented by the general formula [II] on the support and at least one of the cyan couplers represented by the general formula [III].
A silver halide photographic light-sensitive material characterized by containing two in combination. 5. A support containing at least one cyan coupler represented by the general formula [I] and at least one cyan coupler represented by the following general formula [IV] in combination. A silver halide photographic light-sensitive material characterized in that [Chemical 4] [In the formula, R ⁸ represents an unsubstituted alkyl group, and R ⁹ represents a hydrogen atom or a branched or straight-chain alkyl group having 1 to 10 carbon atoms. Further, n is represented by the general formula [II].
Is synonymous with ] 6. A support comprising at least one cyan coupler represented by the general formula [II] and at least one cyan coupler represented by the general formula [IV] in combination. A silver halide photographic light-sensitive material characterized in that