JPH07295171A - Photographic coupler - Google Patents

Abstract

PURPOSE:To provide a photographic coupler to be used as the material of a silver halide color photographic sensitive material and capable of forming a color image not changing hue due to heat, moisture, and light. CONSTITUTION:The photographic coupler is represented by the formula in which R is a substituent; (m) is 0, 1, 2, or 4, and when (m) is 2, 3, or 4, plural R may be the same or different; R1 is H or a substituent; and X is H or a group to be released by reaction with the oxidation product 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 photographic 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, humidity and light. The present invention relates to a photographic coupler that can be used.

[0002]

2. Description of the Related Art Conventionally, when a color photographic image material is generally obtained, a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) is exposed to light and then color-developed. In the above, the oxidized aromatic primary amine color developing agent and the dye-forming coupler react with each other to form a dye, and a color image is formed, but in such a photographic method, a color reproduction method by a subtractive color method is used. Used to form yellow, magenta and cyan color images.

Conventionally, examples of photographic couplers used for forming the above yellow image include acylacetanilide type couplers, and examples of magenta image forming couplers include pyrazolone, pyrazolobenzimidazole, and the like. 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 undergo discoloration or fading 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, are not suitable for the heat resistance and moisture resistance of the formed cyan dye image. However, various proposals have hitherto been made, including selection and search of substituents in couplers, aiming at improvement thereof, but satisfy all requirements for these characteristics. No such coupler has yet been discovered.

On the other hand, a dye formed from a 5-pyrazolone type coupler, which has been widely put to practical use as a magenta color image forming coupler and has been studied, has excellent fastness to heat and light, but has a yellow component. In order to solve this, pyrazolobenzimidazole, indazolone,
Couplers such as pyrazolotriazole, imidazopyrazole, pyrazolopyrazole, and pyrazolotetrazole series have been proposed.In fact, these couplers are preferable from the viewpoint of color reproducibility, but the dye formed from the coupler is an optical dye. It is extremely low in fastness to and has a problem that it tends to cause discoloration and fading.

[0006]

Therefore, in view of the above problems, a first object of the present invention is to provide a photographic coupler used as a material of a silver halide color photographic light-sensitive material, and the first object of the present invention. A second problem is to provide a photographic coupler capable of forming a color image without causing a change in hue due to heat, humidity and light.

[0007]

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

1. A photographic coupler represented by the general formula [I].

[0009]

[Chemical 3]

[In the formula, R represents a substituent, m represents 0 or an integer of 1 to 4, and when m is an integer of 2 or more, a plurality of Rs may be the same or different. R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by the reaction with the oxidation product of the color developing agent. ] 2. A photographic coupler represented by the general formula [II].

[0011]

[Chemical 4]

[Wherein R'represents a substituent, m'represents 0 or an integer of 1 to 4, and when m'is an integer of 2 or more, a plurality of R's are the same or different. May be. R ₁ 'represents a hydrogen atom or a substituent, and X'represents a hydrogen atom or a group which is released by the reaction with the oxidation product of the color developing agent. The present invention will be described in more detail below.

In the general formula [I], the substituent represented by R and R ₁ is not particularly limited, but is typically aliphatic, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cyclo. Each group such as alkyl can be mentioned, but in addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy. , Amino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, heterocyclic thio, and other groups, and spiro compounds Residues, bridged hydrocarbon compound residue and the like are also mentioned.

The present invention will be described in more detail below.

The aliphatic group represented by R and R ₁ may be linear or branched and may be saturated or unsaturated.
Further, this aliphatic group may be substituted with another substituent, and the substituent is not particularly limited, but typically, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cyclo Each group such as alkyl can be mentioned, but in addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy. ,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, heterocyclic thio, and other groups, as well as spiro compound residues and bridges Hydrocarbon compound residues and the like are also included. As an aryl group,
Phenyl, 1-naphthyl and 2-naphthyl groups are preferred.
Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. As the sulfonamide group, an alkylsulfonylamino group,
Aryl sulfonylamino group etc. are mentioned. Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include a linear and branched alkyl group, a phenyl group, a 1-naphthyl group and a 2-naphthyl group, which are further substituted with other substituents. Good. 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 is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an aryl. A phosphonyl group, etc .; as an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .;
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group and the like; as the sulfamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, etc .; Acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; Carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; Ureido group as , An alkylureido group, an arylureido group, etc .; As a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; As a heterocyclic group, a 5- to 7-membered one is preferable. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, a 5- to 7-membered heterocyclic oxy group is preferable, and 3,4,5,6- Tetrahydropyranyl-2-
Oxy group, 1-phenyltetrazole-5-oxy group, etc .; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4 -Diphenoxy-1,3,5-triazine-6-thio group and the like;
As the siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; as the imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; as spiro compound residue Is spiro [3.3] heptan-1-yl, etc .; bridged hydrocarbon compound residues include bicyclo [2.2.
1] heptan-1-yl, tricyclo [3.3.1.137] decane-
1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptane-1-
Ill and the like.

R is preferably aliphatic, aryl,
Acylamino, sulfonamide, halogen atom, acyl, carbamoyl, sulfamoyl, alkoxy, acyloxy, carbamoyloxy, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy groups Is mentioned.

R ₁ is preferably an aliphatic group, an aryl group, an aliphatic oxy group, an acylamino group, an imide group, a sulfonamide group, a sulfamoylamino group, an oxycarbonylamino group or a phosphonylamino group. Can be mentioned.

Examples of the group represented by X which can be eliminated by reacting with the oxidized product of the color developing agent include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycles linked by N atom ring,
Examples include groups such as alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl.
A halogen atom, particularly a chlorine atom and each group of alkoxy, aryloxy, alkylthio and arylthio are preferable.

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

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

Next, synthetic examples of the compound represented by the above general formula [I] will be shown.

[0024]

[Chemical 8]

[Synthesis Example] Synthesis of Exemplified Compound [I-3] (1) Synthesis of Intermediate-1 and Intermediate-2 31 g of 2-amino-3-carbethoxyindole (Helvetica Kimmy Acta) as a starting material (Helv. Chim. Acta),
44, 1748 (1961) described method),
57 g of trimethylorthopalmitate was dissolved in 500 ml of toluene and heated under reflux for 7 hours, and then toluene was distilled off under reduced pressure to obtain Intermediate-1. 600 ml of Intermediate-1 immediately
200m containing 21g of hydroxylamine hydrochloride and 33g of sodium acetate at room temperature.
l of water was added dropwise over 1 hour. After continuing stirring for 2 hours as it was, the reaction solution was distilled off under reduced pressure with ethanol and then extracted with ethyl acetate. The extract was dried over magnesium sulfate, and ethyl acetate was evaporated under reduced pressure to give an oily compound. This was purified by column chromatography to obtain a light yellow powder crystal Intermediate-2. Yield 59 g (86% yield).

(2) Synthesis of Intermediate-3 500 ml of Tetrahydrofuran (T) in which 55 g of Intermediate-2 and 22 g of azidocarboxylic acid ethyl ester were dissolved.
To the (HF) solution, 200 ml of THF in which 32 g of triphenylphosphine was dissolved was added dropwise at room temperature over 2 hours, and after the addition, the reaction solution was further stirred for 10 hours. From the reaction solution under reduced pressure, T
After distilling HF away, the residue was purified by column chromatography to obtain Intermediate-3 which was an off-white powder crystal. Yield 14g
(Yield 25%).

(3) Synthesis of Exemplified Compound I-3 100 ml of 50% aqueous sulfuric acid solution containing 10 g of Intermediate-3 in a suspended state was stirred at 100 ° C. for 3 hours, poured into ice water and extracted with ethyl acetate. The extract was subjected to a reduced pressure treatment to distill off ethyl acetate to obtain Exemplified Compound I-3 as a white powder crystal that precipitates. Yield 6 g (yield 72%). The structure of Exemplified Compound I-3 was confirmed by NMR, IR, and mass spectrum. Exemplified compounds other than Exemplified Compound I-3 were also synthesized according to the above Synthetic Examples, starting from the corresponding starting materials.

Next, the compound represented by the general formula [II] will be described.

In the above formula [II], R'represents a substituent, m'represents 0 or an integer of 1 to 4, and when m'is an integer of 2 or more, a plurality of R's are the same. Or they may be different. R ₁ 'represents a hydrogen atom or a substituent, X'
Represents a hydrogen atom or a group capable of leaving by a reaction with an oxidized product of a color developing agent.

In the above general formula [II], R ', m',
R ₁ 'and X' are each represented by the general formula [I]:
It has the same meaning as R, m, R ₁ and X, and has the above general formula [II].
Specific examples of R ′, R ₁ ′ and X ′ in the above include the groups used as specific examples of R, R ₁ and X in the general formula [I].

Specific examples of the compound according to the general formula [II] of the present invention are shown below, but the present invention is not limited thereto.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

Next, synthetic examples of the compound represented by the above general formula [II] will be shown.

[0036]

[Chemical 12]

[Synthesis Example] Synthesis of Exemplified Compound II-3 (1) Synthesis of Exemplified Compound II-3 3-amino-indazole (Journal of American Chemical Society (J.
Amer. Chem. Soc.), 65, 1804 (1943)), and 28 g of pinacholine bromide.
A solution of 500 ml of acetonitrile containing 28 g of potassium carbonate was heated under reflux for 6 hours, filtered, the filtrate was evaporated under reduced pressure, and the residue was purified by column chromatography.
Exemplified compound II-3, which is an off-white powder crystal, was obtained. yield
20 g (63% yield). The structure of Exemplified Compound II-3 is NM
Confirmed by R, IR, and mass spectrum. Exemplified compounds other than Exemplified Compound II-3 were also synthesized according to the above-mentioned synthesis examples, starting from the corresponding starting materials.

The coupler of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 1 mol per mol of silver halide.
It can be used in the range of ^-1 mol. The photographic 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 photographic coupler of the present invention can be used as a material for forming a color photographic 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 (such as alcohol) and added to the developing solution for use.

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

Typically, a method in which the photographic coupler of the present invention is blended with a silver halide emulsion and the emulsion is coated on a support to form a silver halide color photographic light-sensitive material is preferably used. The photographic coupler of the present invention can be used in negative and positive films and halogenated color photographic light-sensitive materials such as color photographic paper.

The light-sensitive material using the photographic coupler of the present invention such as the color photographic paper may be monochromatic or polychromatic. In the multicolor photosensitive 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 emulsion layer. 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 light-sensitive material is a cyan dye image-forming structural unit (at least one of the cyan couplers is a cyan coupler of the present invention) comprising at least one red light-sensitive silver halide emulsion layer containing at least one cyan coupler. A magenta dye image-forming unit comprising at least one green light-sensitive silver halide emulsion layer containing at least one magenta coupler, and at least one blue light-sensitive silver halide emulsion containing at least one yellow coupler. It consists of a yellow dye image-forming structural unit consisting of layers carried on a support.

The light-sensitive material used in the present invention may have additional layers such as a filter layer, an intermediate layer, a protective layer and an undercoat layer. To incorporate the photographic 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 butyl acetate,
Each of the low boiling point solvents such as butyl propionate is dissolved alone or in a mixture thereof, if necessary, after dissolving the coupler of the present invention alone or in combination, and then mixed with a gelatin aqueous solution containing a surfactant, and then, After emulsifying with a high speed rotary mixer or a colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention.

The silver halide composition preferably used in the light-sensitive material using the photographic 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 fast developability is required. Therefore, it is preferable that the silver halide composition of the silver halide contains a chlorine atom, and at least 1% of silver chloride is contained. Is preferably silver chloride, 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. Silver halide emulsions are known as antifoggants or stabilizers in the photographic industry for the purpose of preventing fog during the manufacturing process of light-sensitive materials, storage, or photographic processing, and / or maintaining stable photographic performance. Existing compounds can be added.

The silver halide color photographic light-sensitive material using the photographic coupler of the present invention includes a color antifoggant, a dye image stabilizer, an ultraviolet absorber, which are usually used in light-sensitive materials.
Antistatic agents, matting agents, surfactants and the like can be used. Regarding these, for example, Research Disclosure, Volume 176, 22-31 (1978
(December year) can be referred to.

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

A silver halide color photographic light-sensitive material using the photographic coupler of the present invention contains a color developing agent in the hydrophilic colloid layer as the color developing agent itself or as a precursor thereof, and is treated with an alkaline activating bath. It can also be processed.

The silver halide color photographic light-sensitive material using the photographic 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.

[0052]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A green 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. In the following examples, the amount of compound added is 1 m ² unless otherwise specified.
(Silver halide is equivalent to silver).

First layer: emulsion layer The following comparative coupler (a) 5.4 × 10 ^-4 mol dissolved in 1.4 g of gelatin, 0.21 g of green-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) and 1.35 g of dioctyl phthalate. A green light-sensitive emulsion layer consisting of.

[0055]

[Chemical 13]

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 so as to be 0.017 g per 1 g of gelatin.

Then, the comparative coupler (a) used in Sample 1 was replaced with the photographic coupler of the present invention shown below (the addition amount was the same molar amount as that of the comparative coupler (a)). Samples 2 to 11 of the present invention were prepared. A hardener, an activator, and an antifungal agent (a mixture of 2-methylisothiazol-3-one and 5-chloro-2-methylisothiazol-3-one) were added to each sample.

The samples 1 to 11 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 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Color developer] Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5.0g Potassium bromide 0.02g Potassium chloride 2.0g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5- Disodium diphosphonate 1.0 g Diethylene glycol 10 g N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline / sulfate 4.5 g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium carbonate 27 g Add water to make the total volume 1 l and adjust to pH 10.10.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Water was added to make a total volume of 1 l, Adjust to pH = 5.7 with potassium carbonate or 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-hydroxyethylidene-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 disulfonic acid derivative) 1.5 g Water to add Is adjusted to 1 liter and pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The concentrations of the samples 1 to 8 treated as described above were measured with a densitometer (KD-7 type manufactured by Konica Corporation), and the treated samples were subjected to high temperature and high humidity (60
The dye image was examined for heat resistance and humidity resistance by allowing it to stand for 14 days in an atmosphere of 80 ° C. and 80% RH. The results are shown below. However, heat resistance
The wettability is expressed by the percentage of residual dye after the heat and humidity test with respect to the initial concentration of 1.0. After irradiating each sample with a xenon fade meter for 100 hours, the density was measured, and the light fastness of the dye image was examined from the dye residual ratio after the light fastness test for the initial density of 1.0. The results are shown below.

Dye Residual Rate (%) Sample No. Coupler used Heat resistance / moisture resistance Light resistance 1 Comparison (a) 87 41 2 Invention (I-2) 90 61 3 Invention (I-3) 88 60 4 Invention (I-4) 92 59 5 Invention ( I-7) 87 55 6 present invention (II-1) 89 56 7 present invention (II-11) 88 58 8 present invention (II-14) 91 60 As is apparent from the above results, the coupler of the present invention is used. The sample used has a significantly improved light resistance and is superior in heat and humidity resistance as compared with the sample using the comparative coupler, so that it can be seen that a robust dye image is formed.

Example 2 A green-sensitive color reversal light-sensitive material (Samples 9 to 14) was prepared by coating each of the following layers on the undercoated triacetyl cellulose film support in order from the support side and containing the couplers shown below. )made.

First layer: emulsion layer 1.4 g of gelatin, green-sensitive silver chlorobromide emulsion (96 mol% of silver chloride)
Content) 0.5 g and a green-sensitive emulsion layer consisting of 7.5 × 10 ⁻⁴ mol of the following coupler dissolved in 1.8 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 so as to be 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 Temperature Time First development 38 ° C 6 minutes Water washing 38 ° C 2 minutes Inversion 38 ° C 2 minutes Color development 38 ° C 6 minutes Adjustment 38 ° C 2 minutes Bleach 38 ° C 6 minutes 38 ° C for 4 minutes Washing with water 38 ° C for 4 minutes Stability at room temperature for 1 minute Drying 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 1000ml [Inversion] 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 Citrazinate 1.5 g N-ethyl-N-β-methanesulfonamidoethyl -3-Methyl-4-aminoaniline / sulfate 11.0 g Ethylenediamine 3.0 g Add water 1000 ml [Preparation liquid] Sodium sulfite 12.0 g Sodium ethylenediaminetetraacetate (dihydrate) 8.0 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water 1000 ml [bleaching solution] Sodium ethylenediaminetetraacetate (dihydrate) 2.0 g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120.0 g Potassium bromide 100.0 g Water is added to 1000 ml [fixing solution] Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water added 1000 ml [Stabilization solution] Formalin (37% by weight) 5 ml Conidax (Konica Corporation) 5 ml Water added 1000 ml Samples treated as above For the same, the light resistance, heat resistance and humidity resistance of the dye image were examined in the same manner as in Example 1. The results are shown below.

Dye Residual Rate (%) Sample No. Coupler used Heat resistance / moisture resistance Light resistance 9 Comparison (a) 90 47 10 Invention (I-10) 91 63 11 Invention (I-15) 93 61 12 Invention (II-4) 92 64 13 Invention ( II-7) 91 62 14 The present invention (II-13) 91 60 As is apparent from the above, the samples using the coupler of the present invention have higher dye residual ratios than the samples using the comparative coupler. It can be seen that it is excellent in heat and humidity resistance and light resistance and is robust.

Example 3 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 of the present invention (II-12) 1.0 g Silver iodobromide (silver equivalent) 0.45 g Polyvinylpyrrolidone 1.0 g Benztriazole 0.02 g Inhibitor * 2 0.001g Thermal solvent * 3 4.5g

[0074]

[Chemical 14]

After imagewise exposure of the above light-sensitive material, it was superposed with an image-receiving material obtained by coating polyvinyl chloride on photographic baryta paper and heat-developed at 150 ° C. for 1 minute to obtain a good image-receiving material. A cyan transfer image was obtained.

[0076]

The photographic coupler according to the present invention can be used as a material of a silver halide color photographic light-sensitive material, and an excellent color image which does not cause a change in hue due to heat, humidity and light can be obtained. It is also effective as a dye-providing substance for photothermographic materials.

Claims (2)

[Claims] 1. A photographic coupler represented by the general formula [I]. [Chemical 1] [In the formula, R represents a substituent, m represents 0 or an integer of 1 to 4, and when m is an integer of 2 or more, plural Rs may be the same or different. R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by the reaction with the oxidation product of the color developing agent. ] 2. A photographic coupler represented by the general formula [II]. [Chemical 2] [In the formula, R'represents a substituent, m'represents 0 or an integer of 1 to 4, and when m'is an integer of 2 or more, a plurality of R's may be the same or different. . R ₁ 'represents a hydrogen atom or a substituent, and X'represents a hydrogen atom or a group which is released by the reaction with the oxidation product of the color developing agent. ]