JPH06236011A - Novel photographic cyan coupler - Google Patents

Abstract

PURPOSE:To provide a novel photographic cyan coupler used as stock of a silver halide color photographic sensitive material and to provide a silver halide color photographic cyan coupler capable of forming a color image which does not cause a change of the hue due to heat, moisture and light. CONSTITUTION:The objective photographic cyan coupler is represented by the general formula, wherein each of R and Y is H or a substituent, EWG is an electron attracting group having >=0.3 Hammett's substituent constant sigmap and X is H or a group releasable by a reaction with the oxidized body 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, a novel photograph capable of forming a dye image having excellent fastness to heat, moisture and light. Cyan coupler for use.

[0002]

BACKGROUND OF THE INVENTION Generally, in the production of color photographs, a silver halide color photographic light-sensitive material is exposed to light and then subjected to color development processing, whereby oxidized primary aromatic compounds are exposed in the exposed areas. 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.

Further, JP-A Nos. 62-278552 and 62-2793.
No. 38 describes an imidazotriazole-based coupler as a magenta coupler, but since it does not have an electron-withdrawing group at the 6-position, the produced dye cannot be a cyan coupler because of a short wave.

In view of such circumstances, the inventors of the present invention further studied and found a photographic coupler capable of forming a dye image which does not change in hue with respect to heat, humidity and light.

[0007]

SUMMARY OF THE INVENTION Therefore, a 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 is to provide a heat-sensitive cyan coupler. -To provide a silver halide color photographic cyan coupler capable of forming a color image without causing a change in hue due to moisture and light.

[0008]

The above objects of the present invention have been achieved by a photographic cyan coupler represented by the general formula [I].

[0009]

[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 present invention will be described in more detail below.

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, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, and the like. Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thiourei Also included are groups such as de, carboxy, hydroxy, mercapto, nitro, and sulfo, 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. A phenyl group is preferred as the aryl 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 preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, 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 .; Acyl groups are alkylcarbonyl groups, arylcarbonyl groups, etc .; Carbamoyl groups are alkylcarbamoyl groups, arylcarbamoyl groups, etc .; Sulfamoyl groups are alkylsulfamoyl groups, arylsulfamoyl groups, etc .; Acyloxy groups are alkyl A carbonyloxy group, an arylcarbonyloxy group, etc .; a sulfonyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, etc .; a carbamoyloxy group, an alkylcarbonyl group, etc. Vamoyloxy group, arylcarbamoyloxy group, etc .; Ureido group is alkylureido group, arylureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is 5 ~
A 7-membered one is preferable, and specifically, 2-furyl group, 2-thienyl 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 and the like; as the heterocyclic thio group,
A 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy group.
-1,3,5-triazole-6-thio group etc .; trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group etc. as siloxy group; succinimide group, 3-heptadecylsuccinimide group as imide group , Phthalimide group, glutarimide group, etc .; spiro [3,3] heptan-1-yl, etc. as spiro compound residue; bicyclo [2,2,1] heptane-1-yl, etc. as bridged hydrocarbon compound residue , tricyclo [3,3,1,1 ^{3 7]} decan-1-yl, 7,7-dimethyl - bicyclo [2,2,1] heptane-1-yl, and the like.

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 (eg, 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 groups (eg ethoxycarbonyl group, phenoxycarbonyl group etc.), 1-tetrazolyl group, 5-chloro-1-tetrazolyl group, carbamoyl group (eg dodecylcarbamoyl group, phenylcarbamoyl group etc.), sulfamoyl group (eg Trifluoromethylsulfamoyl group, phenylsulfamoyl group, ethylsulfamoyl group, etc.) and the like.

Examples of the group capable of splitting off upon reaction with the oxidation product of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkylene, alkoxy, aryloxy, heterocyclic oxy, acyloxy. ,
Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Examples thereof include acylamino, sulfonamide, nitrogen-containing heterocycles bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, but preferably hydrogen atom, halogen atom, alkoxy group, aryloxy group, It is an alkylthio group, an arylthio group, or a nitrogen-containing heterocycle linked by N atoms.

Y represents a hydrogen atom or a substituent, and a preferable substituent is, for example, one that 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. Substituents that are coupled off by a group capable of splitting off under alkaline conditions such as those described in JP-A No. 2003-134, or by reaction with an oxidized product of a developing agent as described in JP-A-56-133734. Etc., but preferably Y is 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.

[0022]

[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.

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

The compounds of the present invention are described in JC Perkin II, pages 4 to 11 (1972), JCSChem.Commun. 1524 to 1525 (1970), Tetrahedron Vol. 32, pages 341 to 348 (197).
6 years), Ukr.J.Chem. 44, 725-729 (1978),
It can be synthesized according to the synthetic method described in Vol. 39, pp. 1289-1290 (1973).

[Synthesis Example] Exemplified compound (17) was synthesized by the following route.

[0032]

[Chemical 10]

Synthesis of Exemplified Compound (17) 19.1 g (0.1 mol) of (17a) and 44.9 g (0.1 mol) of (17
b) (synthesized according to the synthetic method described in JCS pages 4508 to 4510 (1954)) in 300 ml of ethanol with heating under reflux.
React for hours.

After completion of the reaction, ethyl acetate and water are added, the organic layer is extracted, dried and the solvent is distilled off under reduced pressure. Then, the obtained residue is recrystallized from acetonitrile to obtain 33.5 g (yield 62%) of the target Exemplified compound (17).

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 green light-sensitive silver halide emulsion layer and / or 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 production 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.

[0055]

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 a compound is per 1 m ² (silver halide is a silver conversion value).

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

Second layer: protective layer A protective layer containing 0.50 g of gelatin. As a hardening agent, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added so that the amount was 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 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 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-fix 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 0.2g 1,2-benzisothiazolin-3-one 0.3g ethylene glycol 1.0g 1-dihydroxyethylidene-1,1-diphosphonic acid 2.0g o-Phenylphenol sodium 1.0g Ethylenediaminetetraacetic acid 1.0g Ammonium hydroxide (20% aqueous solution) 3.0g Optical brightener (4,4-diaminostilbene sulfonic acid derivative) 1.5g Add water 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 8 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) 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 remaining after the heat, humidity and light resistance test with respect to the initial density of 1.0.

[0067]

[Chemical 11]

[0068]

[Table 1]

As is clear from the results shown in Table 1, the samples using the coupler of the present invention have a higher dye residual rate than the samples using the comparative coupler, and are excellent in heat resistance, humidity resistance and light resistance. It turns out that it is robust.

Example 2 The following layers were sequentially coated on the undercoated triacetate film from the support side to prepare a red color photosensitive 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 Comparative cyan coupler b 8.0 × 10 ⁻ dissolved in 1.4 g of gelatin, 1.5 g of red-sensitive silver iodobromide emulsion (containing 4 mol% of silver iodide) and 1.1 g of tricresyl phosphate. ^A red-sensitive emulsion layer consisting of ⁴ moles.

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 comparative coupler b in Sample 9 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.

[0075]

[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 Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 The composition of the treatment liquid used in each treatment 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 iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to 1000 ml, and the pH is adjusted to 6.0 with ammonia water.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Water is added to make 1000 ml, and pH is 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 above-treated samples 9 to 16 were measured using a densitometer (Konica Corporation KD-7 type), and the treated samples were subjected to high temperature / 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.

Further, 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 remaining after the heat, humidity and light resistance test with respect to the initial density of 1.0.

Further, 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.

[0083]

[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 the dye and are superior in heat resistance, moisture resistance and light resistance to the sample using the comparative coupler b. It can be seen that it is excellent and also excellent in color reproducibility.

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 triacetylcellulose 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, 0.5 g of red-sensitive silver chlorobromide emulsion (containing 96 mol% of silver chloride) and 1.5 g of dibutyl phthalate dissolved in Table 3
A red-sensitive emulsion layer consisting of 9.1 × 10 ⁻⁴ mol of the coupler shown in FIG.

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 processing step] Processing step 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 0.1g Sodium hydroxide 5.0g Glacial acetic acid 15ml Water added 1000ml [Color developer] Sodium tetrapolyphosphate 2.0g Sodium sulfite 7.0g Sodium triphosphate (12-hydrate) 36.0g Potassium bromide 1.0g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoanili・ Sulfate 11.0g Ethylenediamine 3.0g Water added 1000ml [Adjustment] Sodium sulfite 12.0g Sodium ethylenediaminetetraacetate (dihydrate) 8.0g Thioglycerin 0.4ml Glacial acetic acid 3ml Water added 1000ml [Bleach] Sodium ethylenediaminetetraacetate (dihydrate) 2.0 g Ethylenediaminetetraacetate iron (III) ammonium (dihydrate) 120.0 g Potassium bromide 100.0 g Water is added to 1000 ml [fixing solution] Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5g Water added 1000ml [Stabilization liquid] Formalin (37% by weight) 5ml Conidax (Konica Corporation) 5ml Water added 1000ml Similar to Example 2, heat resistance of dye image for each sample treated above -The moisture resistance and light resistance were examined. The results are shown in Table 3.

[0092]

[Table 3]

As is clear from Table 3, the sample using the coupler of the present invention is
It can be seen that all of them have a high dye residual ratio, are excellent in heat resistance, humidity resistance and light resistance and are robust.

Example 4 On a transparent polyethylene terephthalate film support,
A photothermographic layer comprising the following constituents was applied per 1 m ^{2 of the} support to prepare a photothermographic material.

Benztriazole silver 0.6 g Gelatin 3.0 g Reducing agent * 1 0.97 g Coupler (35) 1.0 g Silver iodobromide (silver equivalent) 0.45 g Polyvinylpyrrolidone 1.0 g Benztriazole 0.02 g Inhibitor * 2 Thermal solvent * 3 4.5 g After imagewise exposing the above light-sensitive material, superimposing it on an image-receiving material obtained by coating polyvinyl chloride on photographic variator paper,
When heat development was carried out at 150 ° C. for 1 minute, a good cyan transfer image was obtained on the image receiving material.

[0096]

[Chemical 13]

[0097]

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, a change in hue caused by heat, humidity and light. It is possible to provide a silver halide color photographic cyan coupler capable of forming a color image which does not occur.

Claims (1)

[Claims] 1. A photographic cyan coupler represented by the general formula [I]: [Wherein R and Y represent a hydrogen atom or a substituent, and E
WG 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 oxidized product of a color developing agent. ]