JPH0792632A - Novel photographic cyan coupler - Google Patents

Abstract

PURPOSE:To provide a novel photographic cyan coupler to be used as the elemental material of a silver halide photographic sensitive material which has superior color reproduction performance and can form a color image not causing hue change due to heat and humidity, and light. CONSTITUTION:The photographic cyan coupler to be used is represented by the formula in which each of R and Y is H or a substituent; EWG is an electron-attractive group having a Hammett's substituent constant deltap of >=0.3; and X is H or a group to be released by reaction with the oxidation component of a color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyan coupler used as a material for a silver halide color photographic light-sensitive material, and more specifically, it forms a dye image excellent in color reproducibility and fastness to heat, moisture and light. The present invention relates to a new photographic cyan coupler that can be used.

[0002]

2. Description of the Related Art Generally, in the case of producing a color photograph, a silver halide color photographic light-sensitive material is exposed to light and then subjected to color development processing. Amine color developing agents and dye-forming couplers react to form dyes to form color images, but in such photographic methods a subtractive color reproduction method is used, whereby yellow, magenta and cyan are used. An image of each color is formed.

Conventionally, as a photographic coupler used for forming the above yellow color image, there is, for example, an acylacetanilide type coupler, and as a magenta color image forming coupler, for example, pyrazolone, pyrazolobenzimidazole, Pyrazolotriazole or indazolone couplers are known, and as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used,
It is desired that the dye image obtained from these couplers does not deteriorate even when exposed to light for a long time or stored at high temperature and high humidity.

However, the above-mentioned phenol-based couplers and naphthol-based couplers, which have been studied and put into practical use as couplers for forming cyan dyes, have the spectral absorption characteristics of the formed cyan dye image,
It is still insufficient in terms of heat resistance and moisture resistance, and therefore various proposals have been made in the past, including the selection and search of substituents in couplers, with the aim of improving this. No coupler has been found that satisfies all requirements.

Research Disclosure (Re
serch Disclosure) 16216 describes an imidazotriazole-based coupler as a cyan coupler, but it does not have an electron-withdrawing group at the 6-position, so the suction of the produced dye is shortwave and not satisfactory for color reproduction. .

The present inventors have conducted further research in view of such circumstances, and as a result, they are excellent in color reproducibility and are capable of forming a dye image that does not cause a hue change with respect to heat, humidity and light. Found.

[0007]

Therefore, the first object of the present invention is to provide a novel photographic cyan coupler used as a raw material of a silver halide color photographic light-sensitive material, and a second object of the present invention. It is an object of the present invention to provide a silver halide color photographic cyan coupler having excellent color reproducibility and capable of forming a color image which does not cause a change in hue due to heat, moisture and light.

[0008]

The above object of the present invention has been achieved by the following constitution or.

A photographic cyan coupler represented by the general formula [I]

[0010]

[Chemical 2]

In the formula, R and Y represent a hydrogen atom or a substituent, EWG represents an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.3 or more, and X represents a hydrogen atom or an oxidized product of a color developing agent. Represents a group capable of leaving by the reaction of.

The EWG of the compound represented by the above general formula [I] is arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, β, β-dicyanovinyl group, halogenated alkyl group, formyl group, arylcarbonyl group, aryloxy group. The photographic cyan coupler according to claim 1, which is a carbonyl group, a monoalkylcarbamoyl group, a monoarylcarbamoyl group, a monoalkylsulfamoyl group, or a monoarylsulfamoyl group.

The present invention will be specifically described below.

First, the cyan coupler of the present invention represented by the general formula [I] will be described.

In the general formula [I], the substituent represented by R is not particularly limited, but typically, each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples thereof include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl,
Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy,
Heterocyclicoxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino,
Imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Examples also include alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro and sulfo groups, as well as spiro compound residues and bridged hydrocarbon compound residues.

Hereinafter, in each group represented by R, the alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group is preferably a phenyl group.

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

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

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

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

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred. Alkylsulfonyl group, arylsulfonyl group, etc. as sulfonyl group; alkylsulfinyl group, arylsulfinyl group, etc. as sulfinyl group; alkylphosphonyl group, alkoxyphosphonyl group, aryloxyphosphonyl group, arylphosphonyl group as phosphonyl group Etc .; as the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group or the like; the sulfamoyl group is an alkylsulfamoyl group, an arylsulfamoyl group or the like;
An alkylcarbonyloxy group as the acyloxy group,
Arylcarbonyloxy group, etc .; Sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; Ureido group, alkylureido group, arylureido group, etc. Etc .; as a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, 2-thienyl group Group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .; as a heterocyclic thio group, 5 To 7-membered heterocyclic thio groups are preferred, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group; siloxy group is trimethyl. Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. as imide group; spiro compound residue as spiro [3,3 ] Heptane
-1-yl, etc .; bridged hydrocarbon compounds
[2,2,1] Heptan-1-yl, tricyclo [3,3,1,1 ^{3 7} ]
Examples include decane-1-yl and 7,7-dimethyl-bicyclo [2,2,1] heptan-1-yl.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

In the general formula [I], the substituent represented by EWG is a substituent having a Hammett's substituent constant σ _p of 0.3 or more, and is typically a cyano group, a nitro group or a sulfonyl group (eg, octylsulfonyl). Group, phenylsulfonyl group, tolufluoromethylsulfonyl group, pentafluorophenylsulfonyl group, etc.), β-carboxyvinyl group, sulfinyl group (for example, t-butylsulfinyl group,
Tolylsulfinyl group, trifluoromethylsulfinyl group, pentafluorophenylsulfinyl group, etc.),
β, β-dicyanovinyl group, halogenated alkyl group (eg trifluoromethyl group, perfluorooctyl group,
ω-hydroperfluorododecyl group, etc.), formyl group,
Carboxyl group, carbonyl group (eg acetyl group, pivaloyl group, benzoyl group, trifluoroacetyl group etc.), alkyl and aryloxycarbonyl group (eg ethoxycarbonyl group, phenoxycarbonyl group etc.), 1-tetrazolyl group, 5-chloro- 1-tetrazolyl group, carbamoyl group (for example, dodecylcarbamoyl group,
Phenylcarbamoyl group, etc.), a sulfamoyl group (eg, a trifluoromethylsulfamoyl group, a phenylsulfamoyl group, an ethylsulfamoyl group, etc.) and the like.

Preferred substituents represented by EWG are:
Arylsulfonyl group (for example, phenylsulfonyl group,
Pentafluorophenylsulfonyl group, etc.), alkylsulfinyl group (eg t-butylsulfinyl group, trifluoromethylsulfinyl group etc.), arylsulfinyl group (eg tolylsulfinyl group, pentafluorophenylsulfinyl group etc.), β, β-dicyanovinyl Base,
Halogenated alkyl group (eg trifluoromethyl group,
Perfluorooctyl group etc.), formyl group, arylcarbonyl group (eg benzoyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), monoalkylcarbamoyl group (eg dodecylcarbamoyl group etc.), monoarylcarbamoyl group (eg Phenylcarbamoyl group, etc.), monoalkylsulfamoyl group (eg, trifluoromethylsulfamoyl group, ethylsulfamoyl group, etc.) and monoarylsulfamoyl group (eg, phenylsulfamoyl group, etc.) .

Examples of the group represented by X, which can be split off by the reaction with the oxidation product of the color developing agent, include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkylene, alkoxy, aryloxy, heterocyclic oxy, acyloxy. , Sulfonyloxy, alkoxycarbonyloxy,
Aryloxy carbonyl, alkyl oxalyl oxy, alkoxy oxalyl oxy, alkyl thio, aryl thio, heterocyclic thio, alkyloxy thiocarbonyl thio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxy carbonylamino, aryloxy Each group such as carbonylamino and carboxyl is exemplified, but preferably a hydrogen atom, a halogen atom,
It is an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a nitrogen-containing heterocycle linked by N atoms.

Y represents a hydrogen atom or a substituent. A preferred substituent is, for example, one which is eliminated after reacting with an oxidized product of a developing agent. For example, the substituent represented by Y is described in JP-A-61-228444. Under alkaline conditions such as those described in JP-A-56-133, by a reaction with a group capable of splitting off and an oxidized product of a developing agent as described in JP-A-56-133734,
Examples of the substituent include coupling-off and the like, and Y is preferably a hydrogen atom. Therefore, among the compounds of the present invention represented by the general formula [I], the compound represented by the general formula [II] is particularly preferable.

[0028]

[Chemical 3]

[In the formula, R, X and EWG have the same meanings as R, X and EWG in the general formula [I]. Next, representative compound examples of the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

The compounds of the present invention are described in Chem. Ber. Vol.
45 to 2852 (1970), 103, 3533 to 3542 (1970), 105, 1810 to 1814 (1972), Te
trahedron Vol. 32, pp. 341-348 (1976), J. Chem. Res
Each (s) can be synthesized according to the synthetic method described on pages 262 to 263 (1989).

[Synthesis Example] Exemplified compound (16) was synthesized by the following route.

[0038]

[Chemical 10]

(Synthesis of Intermediate (16c)) 7.57 g of (16a)
(30 mmol) and 5.73 g (30 mmol) of (16b) were dissolved in 100 ml of acetonitrile, and 5.88 g (30 mmol) of 28% methanol solution of sodium methylate was added dropwise at room temperature under a nitrogen stream. After further stirring for 2 hours at room temperature, the mixture was neutralized with hydrochloric acid and extracted with ethyl acetate. After drying, the solvent was distilled off under reduced pressure and the residue was separated by column chromatography to obtain 4.47 g (yield 41%) of intermediate (16c).

(Synthesis of Exemplified Compound (16)) Intermediate (16
c) 3.62 g (10 mmol) is reacted with 40 ml of toluene and 2.80 ml (30 mmol) of phosphorus oxychloride under heating under reflux for 5 hours. After completion of the reaction, the reaction solution was poured into ice-water and extracted with ethyl acetate. After drying, the solvent was distilled off under reduced pressure, the residue was separated by column chromatography, and the exemplary compound (1
2.48 g (yield 72%) of 6) was obtained.

The structure is ¹ H-NMR, IR, MAS
Confirmed by S spectrum.

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

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

The methods and techniques used in conventional dye-forming couplers are likewise applied to the couplers of this invention.

The coupler of the present invention can be used as a material for forming a color photograph by any coloring method, and specific examples thereof include an external coloring method and an internal coloring method. When used as an external color-developing method, the coupler of the present invention can be dissolved in an aqueous alkali solution or an organic solvent (eg alcohol) and added to the developing solution for use.

When the coupler of the present invention is used as a color photographic material by the internal color forming method, the coupler of the present invention is used by incorporating it in a photographic light-sensitive material.

Typically, a method in which the coupler of the present invention is blended with a silver halide emulsion and the emulsion is coated on a support to form a color light-sensitive material is preferably used.

The coupler of the present invention is used in color photographic light-sensitive materials such as color negative and positive films and color photographic paper.

The light-sensitive material using the coupler of the present invention, such as this color photographic paper, may be monochromatic or multicolor. 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 comprising at least one red-sensitive silver halide emulsion layer containing one cyan coupler, and a magenta dye image comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler. Forming building block, at least 1 (at least one of the cyan couplers is a coupler of the invention).
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, storage or 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.

[0062]

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 from the support side on a paper support laminated on both sides with polyethylene. 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.

Then, the sample 2 of the present invention was prepared in exactly the same manner as the sample 1 except that the comparative coupler a in the sample 1 was replaced with the coupler shown in Table 1 (the addition amount was the same molar amount as the comparative coupler a).
~ 8 were produced.

The samples 1 to 8 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 solution 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 above-treated samples 1 to 8 were measured using a densitometer (KD-7 type manufactured by Konica Corporation), and the treated samples were subjected to high temperature and high humidity (60 ° C., 80
% RH) and left for 14 days to examine the heat and humidity resistance of the dye image.

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, humidity resistance and light resistance of the dye image are expressed by the percentage of dye residue after the heat, humidity and light resistance tests for the initial density of 1.0.

[0074]

[Chemical 11]

[0075]

[Table 1]

As is clear from the results shown in Table 1, all of the samples using the coupler of the present invention, Samples 4 to 8, had a higher dye residual ratio and higher heat and humidity resistance than the samples using the comparative coupler. It can be seen that the film has excellent light resistance and is robust.

Example 2 The following layers were sequentially coated on the undercoated triacetate film from the support side to prepare a red light-sensitive color light-sensitive material (Sample 9). The addition amount of the compound is per 1 m ² unless otherwise specified (silver halide is equivalent to silver).

First layer: emulsion layer 1.4 g of gelatin, red-sensitive silver iodobromide emulsion (4 mol% of silver iodide)
Containing) were dissolved in 1.5g and tricresyl phosphate 1.1 g, Comparative Cyan Coupler b 8.0 × 10 ^-4 consisting mol red-sensitive emulsion layer.

Second layer: protective layer A protective layer containing 1.5 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 Sample 9, except that the coupler shown in Table 2 was replaced by the coupler shown in Table 2 (the addition amount was the same molar amount as that of Comparative coupler b), Sample 10 of the present invention was used.
~ 16 were made.

The obtained film sample was subjected to wedge exposure by a usual method, and color development was performed according to the following color processing steps.

[0082]

[Chemical 12]

[Treatment process] (Treatment temperature 38 ° C.) Treatment time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute Dry for 30 seconds The composition of the processing solution used in each processing step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitriloacetic acid trisodium (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1000 ml, and the pH is adjusted to 10.6 using sodium hydroxide.

[Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Add water to make 1000 ml, and adjust to pH 6.0 with ammonia water. .

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water was added to make 1000 ml, and pH was adjusted to 6.0 with acetic acid.

[Stabilizing Solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corp.) 7.5 ml Water is added to make 1000 ml.

The transmission densities of the samples 9 to 16 treated as described above were measured using a densitometer (Konica Corporation KD-7 type), and the treated samples were treated at high temperature and high humidity (60 ° C., 8
It was left for 14 days in an atmosphere of 0% RH) and the heat resistance and humidity resistance of the dye image were examined.

Also, each sample was irradiated with a xenon fade meter for 10 days to examine the light resistance. The results are shown in Table 2. However, the heat resistance, humidity resistance and light resistance of the dye image are expressed by the percentage of dye residue after the heat, humidity and light resistance tests for the initial density of 1.0.

Also, the color image sample was stretched 10 times on Konica color paper and subjected to color paper development processing (CPK
-18P) was performed, and the color reproducibility was visually evaluated on a 5-point scale. The larger the value, the better the color reproducibility.

[0091]

[Table 2]

As is clear from the results shown in Table 2, the samples using the coupler of the present invention have a higher residual ratio of dye, and are superior in heat resistance, humidity resistance and light resistance to the samples using the comparative coupler b. It can be seen that it is excellent and also excellent in color reproducibility. In particular, samples 13 to 16 using the coupler of the present invention are found to have excellent fastness.

Samples using the coupler of the present invention are
It can be seen that the color reproducibility is superior to the sample using the comparative coupler c.

Example 3 The following layers were sequentially coated on a triacetyl cellulose film support from the support side to prepare red-sensitive color reversal photographic light-sensitive materials 17 to 22 containing the couplers shown in Table 3.

First layer: Emulsion layer 1.4 g of gelatin, red-sensitive silver chlorobromide emulsion (96 mol% of silver chloride)
Content) 0.5 g and a red-sensitive emulsion layer consisting of 9.1 × 10 ⁻⁴ mol of the coupler shown in Table 3 dissolved in 1.5 g of dibutyl phthalate.

Second layer: protective layer A protective layer containing 0.5 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.

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

[Reversal Treatment Process] Treatment Process Time Temperature First development 6 minutes 38 ° C. Water washing 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. adjustment 2 minutes 38 ° C. Bleach 6 minutes 38 ° C. fixed 4 minutes 38 ℃ Washing with water 4 minutes 38 ℃ Stability 1 minute Drying at room temperature Use the following composition of the treatment liquid.

[First developer] Sodium tetrapolyphosphate 2.0 g Sodium sulfite 20.0 g Hydroquinone monosulfonate 30.0 g Sodium carbonate (monohydrate) 30.0 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml [Resolution] Nitrilotrimethylenephosphonic acid 6-sodium salt 3.0g Stannous chloride (dihydrate) 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 5.0 g Glacial acetic acid 15 ml Water added 1000 ml [Color developer] Sodium tetrapolyphosphate 2.0 g Sodium sulfite 7.0 g Sodium triphosphate (12-hydrate) 36.0 g Potassium bromide 1.0 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl -4-Aminoaniline / sulfate 11.0g Ethylenediamine 3.0g Add water 1000ml [Preparation] Sodium sulfite 12.0g Sodium ethylenediaminetetraacetate (dihydrate) 8.0g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml [Bleaching solution] Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120.0g Potassium bromide 100.0g Water is added to 1000ml [Fixing solution] Ammonium thiosulfate 80g Sulfite Sodium 5g Sodium bisulfite 5g Water added 1000ml [Stabilization solution] Formalin (37wt%) 5ml Conidax (Konica Corporation) 5ml Water added 1000ml Same as Example 2 for each sample treated above The heat resistance, humidity resistance and light resistance of the dye image were examined. The results are shown in Table 3.

[0100]

[Table 3]

As is clear from Table 3, the samples using the coupler of the present invention, Samples 19 to 22, all had a higher dye residual ratio, heat resistance, humidity resistance and light resistance than the samples using the comparative coupler. It can be seen that it has excellent properties and is robust.

[0102]

According to the present invention, firstly, there is provided a novel photographic cyan coupler used as a material for a silver halide color photographic light-sensitive material, and secondly, it is excellent in color reproducibility and has good heat, humidity and light. It is possible to provide a silver halide color photographic cyan coupler capable of forming a color image without causing a change in hue due to the above.

Claims (2)

[Claims] 1. A photographic cyan coupler represented by the general formula [I]: [In the formula, R and Y represent a hydrogen atom or a substituent,
EWG represents an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.3 or more, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of a color developing agent. ] 2. The EWG of the compound represented by the general formula [I] is arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, β, β-dicyanovinyl group, halogenated alkyl group, formyl group, arylcarbonyl group, The photographic cyan coupler according to claim 1, which is an aryloxycarbonyl group, a monoalkylcarbamoyl group, a monoarylcarbamoyl group, a monoalkylsulfamoyl group, or a monoarylsulfamoyl group.