JP3245761B2 - Photo coupler - Google Patents

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 particularly to a dye image having excellent color reproducibility and fastness to heat, humidity and light. It relates to a possible photographic coupler.

[0002]

2. Description of the Related Art Conventionally, in general, when a color photographic image material is 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 reacts with the dye-forming coupler to form a dye, and a color image is formed.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, photographic couplers used for forming the yellow image include, for example, acylacetanilide couplers, and magenta image forming couplers include, for example, pyrazolone and pyrazolobenzimidazole. Pyrazolotriazole or indazolone couplers are known, and as a coupler for cyan image formation, for example, phenol or naphthol couplers are generally used,
It is desired that the dye images obtained from these couplers do not discolor even if exposed to light for a long time or stored under high temperature and high humidity.

[0004] However, as couplers for forming cyan dyes, the above-mentioned phenol couplers and naphthol couplers, which have been studied and put to practical use, have been developed in consideration of heat resistance and moisture resistance of the formed cyan dye image. However, various proposals have been made in the past, including the selection and exploration of substituents in couplers, with the aim of improving this, but all the requirements regarding these properties are satisfied. No such coupler has been found yet.

On the other hand, dyes formed from 5-pyrazolone-based couplers which have been widely and practically used as magenta image forming couplers and which have been studied are excellent in fastness to heat and light, but have a yellow component. Because it has unnecessary absorption that causes color turbidity, in order to solve this, pyrazorobenzimidazole, indazolone,
Couplers such as pyrazolotriazole, imidazopyrazole, pyrazolopyrazole and pyrazolotetrazole have been proposed.In fact, although these couplers are preferable from the viewpoint of color reproducibility, the dye formed from the coupler is light-sensitive. Has a problem in that the fastness to the toner is remarkably low and discoloration is easily caused.

[0006]

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

[0007]

The above object of the present invention is achieved by the following constitution.

[0008] 1. A photographic coupler represented by the general formula [I].

[0009]

Embedded image

[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 Rs may be the same or different. R ₁ represents a hydrogen atom or a substituent; X represents a hydrogen atom or a group which is eliminated by a reaction with an oxidized form of a color developing agent. ] 2. A photographic coupler represented by the general formula [II].

[0011]

Embedded image

[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 different even if they are the same. You may. R ₁ ′ represents a hydrogen atom or a substituent, and X ′ represents a hydrogen atom or a group which is released by a reaction with an oxidized form of a color developing agent. Hereinafter, the present invention will be described more specifically.

In the general formula [I], the substituents represented by R and R ₁ are not particularly limited, but are typically aliphatic, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Examples of each group include alkyl and the like, and in addition thereto, 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, etc., and spiro compounds Residues, bridged hydrocarbon compound residue and the like are also mentioned.

Hereinafter, the present invention will be described in more detail.

The aliphatic groups represented by R and R ₁ may be linear or branched, and may be saturated or unsaturated.
The aliphatic group may be substituted with another substituent, and the substituent is not particularly limited, but typically, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl Examples of each group include alkyl and the like, and in addition thereto, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, heterocycle oxy, siloxy, acyloxy, carbamoyloxy ,
Each group such as amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hydroxy, carboxy, heterocyclic thio, and spiro compound residue, bridged Hydrocarbon compound residues are also included. As the aryl group,
A phenyl group, a 1-naphthyl group and a 2-naphthyl group are preferred.
Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group,
Arylsulfonylamino group and the like. Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include linear and branched alkyl groups, phenyl groups, 1-naphthyl groups, and 2-naphthyl groups, which are further substituted with other substituents. Is also good. The alkenyl group is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched.
The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms. Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an aryloxy group. A phosphonyl group or the like; acyl groups such as an alkylcarbonyl group and an arylcarbonyl group;
Examples of the carbamoyl group include an alkylcarbamoyl group and an arylcarbamoyl group.
Alkylsulfamoyl group, arylsulfamoyl group, etc .; acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .; ureido group , An alkylureido group, an arylureido group, etc .; as the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; and as the heterocyclic group, a 5- to 7-membered group is preferable. A 2-furyl group, a 2-thienyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group and the like; As the heterocyclic oxy group, a 5- to 7-membered heterocyclic oxy group is preferable, and 3,4,5,6- Tetrahydropyranyl-2-
An oxy group, a 1-phenyltetrazole-5-oxy group or the like; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4 -Diphenoxy-1,3,5-triazine-6-thio group and the like;
As a siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; As an imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc .; as a spiro compound residue Is spiro [3.3] heptane-1-yl and the like; as a bridged hydrocarbon compound residue, bicyclo [2.2.
1] Heptan-1-yl, tricyclo [3.3.1.137] decane-
1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptane-1-
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 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. No.

Examples of the group capable of leaving by reacting with the oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a bromine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heteroatom linked by N atom ring,
Alkyloxycarbonylamino, aryloxycarbonylamino, each group such as carboxyl,
Preferable are a halogen atom, particularly a chlorine atom, and alkoxy, aryloxy, alkylthio and arylthio groups.

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

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

Next, a synthesis example of the compound represented by the above general formula [I] will be shown.

[0024]

Embedded image

[Synthesis Example] Synthesis of Exemplified Compound [I-3] (1) Synthesis of Intermediate-1 and Intermediate-2 2-amino-3-carbethoxyindole (Helvetica Kimmy Acta) which is a raw material of 31 g (Helv. Chim. Acta),
44, 1748 (1961)) and
57 g of trimethyl orthopalmitate 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
After dissolving in ethanol at room temperature, 200 m containing 21 g of hydroxylamine hydrochloride and 33 g of sodium acetate were added thereto at room temperature.
l of water was added dropwise over 1 hour. After stirring was continued for 2 hours as it was, the reaction solution was distilled off under reduced pressure with ethanol, and extracted with ethyl acetate. After the extract was dried over magnesium sulfate, ethyl acetate was distilled off under reduced pressure to obtain an oily compound. This was purified by column chromatography to obtain Intermediate-2 which was a pale yellow powder crystal. Yield 59 g (86% yield).

(2) Synthesis of Intermediate-3 55 ml of Intermediate-2 and 22 g of ethyl azidocarboxylate were dissolved in 500 ml of tetrahydrofuran (T
To the HF) solution, 200 ml of THF in which 32 g of triphenylphosphine was dissolved was added dropwise over 2 hours at room temperature, and after the addition, the reaction solution was further stirred for 10 hours. Under reduced pressure, T
After evaporating HF, 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 a 50% aqueous sulfuric acid solution containing 10 g of Intermediate-3 in suspension was stirred at 100 ° C. for 3 hours, poured into ice water and extracted with ethyl acetate. The extract was treated under reduced pressure to remove ethyl acetate, thereby obtaining Exemplified Compound I-3 as a white powder crystal to be precipitated. Yield 6 g (72% yield). 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 Synthesis Examples, starting from the corresponding raw materials.

Next, the compound represented by formula (II) will be described.

In the general 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 different. R ₁ ′ represents a hydrogen atom or a substituent, and X ′
Represents a hydrogen atom or a group which is released by a reaction with an oxidized form of a color developing agent.

In the 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 general formula [II]
Examples of R ′, R ₁ ′ and X ′ in formula (I) include the groups used as specific examples of R, R ₁ and X in formula (I).

Hereinafter, specific examples of the compound represented by the general formula [II] of the present invention will be shown, but the present invention is not limited thereto.

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

Next, a synthesis example of the compound represented by the above general formula [II] will be shown.

[0036]

Embedded image

[Synthesis Example] Synthesis of Exemplified Compound II-3 (1) Synthesis of Exemplified Compound II-3 3-amino-indazole which is a raw material of 21 g (Journal of American Chemical Society (J.
Amer. Chem. Soc.), 65, 1804 (1943)), 28 g of pinacolin 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 distilled off under reduced pressure, and the residue was purified by column chromatography.
Exemplified compound II-3 was obtained as an off-white powder crystal. yield
20 g (63% yield). The structure of the exemplified compound II-3 is represented by NM
Confirmed by R, IR and mass spectrum. Exemplified compounds other than Exemplified Compound II-3 were also synthesized according to the above Synthesis Examples, starting from the corresponding raw materials.

The coupler of the present invention is usually used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 per mol of silver halide.
It can be used in the range of ^-1 mol. Further, the photographic coupler of the present invention can be used in combination with another type of cyan coupler.

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

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

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

Typically, a method of forming a silver halide color photographic light-sensitive material by incorporating the photographic coupler of the present invention into a silver halide emulsion and coating the emulsion on a support is preferably used. The photographic coupler of the present invention is used for, for example, halogenated color photographic light-sensitive materials such as negative and positive films and color printing paper.

The light-sensitive material using the photographic coupler of the present invention such as the color photographic paper may be of a single color or a multicolor. In a multicolor light-sensitive material, the coupler of the present invention may be contained in any layer, but is usually contained in a red-sensitive silver halide emulsion layer. The multicolor light-sensitive material has a dye image-forming constituent unit having photosensitivity in each of three primary color regions of the spectrum. Each structural unit can be composed 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 comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler (at least one of the cyan couplers is a cyan coupler of the present invention). Magenta dye image-forming units comprising at least one green-sensitive silver halide emulsion layer containing at least one magenta coupler, at least one blue-sensitive silver halide emulsion containing at least one yellow coupler It consists of a yellow dye image forming structural unit comprising a layer 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, an undercoat layer and the like. The photographic coupler of the present invention can be incorporated into an emulsion by a conventionally known method. For example, tricresyl phosphate, a high-boiling organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate or butyl acetate,
After dissolving the coupler of the present invention alone or in combination with a low-boiling solvent such as butyl propionate alone or, if necessary, in a mixture thereof, and mixing with a gelatin aqueous solution containing a surfactant, After emulsification with a high-speed rotary mixer or a colloid mill, the mixture can be added to silver halide to prepare a silver halide emulsion used in the present invention.

The silver halide composition preferably used for the light-sensitive material using the photographic coupler of the present invention includes silver chloride, silver chlorobromide or silver chloroiodobromide. Further, a combination mixture such as a mixture of silver chloride and silver bromide may be used.
That is, when a silver halide emulsion is used for color printing paper, particularly fast developability is required. Therefore, the silver halide composition of the silver halide preferably contains a chlorine atom, and at least 1% of silver chloride. Is preferably silver chloride, silver chlorobromide or silver chloroiodobromide.

The silver halide emulsion is chemically sensitized by a conventional method. Also, 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 production process, storage, or photographic processing of light-sensitive materials, and / or maintaining stable photographic performance. Can be added.

The silver halide color photographic light-sensitive material using the photographic coupler of the present invention includes a color fogging inhibitor, a dye image stabilizer, an ultraviolet absorber, which are usually used in light-sensitive materials.
An antistatic agent, a matting agent, a surfactant and the like can be used. These are described, for example, in Research Disclosure, Vol. 176, pp. 22-31 (1978).
December) can be referred to.

The silver halide color photographic material using the photographic coupler of the present invention can form an image by performing a color development process known in the art.

The 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 provided with an alkaline activating bath. It can also be processed.

The silver halide color photographic material using the photographic coupler of the present invention is subjected to bleaching and fixing 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 stabilization treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0052]

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

Example 1 The following layers were sequentially coated on a paper support laminated on both sides with polyethylene from the support side, and a green photosensitive color photosensitive material sample 1 was prepared. In addition, in the following Examples, the addition amount of a compound is shown per 1 m ² unless otherwise specified.
(Silver halide is silver equivalent).

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

[0055]

Embedded image

Second layer: protective layer A protective layer containing 0.50 g of gelatin. In addition, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardening agent so as to be 0.017 g per 1 g of gelatin.

Next, the same procedure was repeated except that the comparative coupler (a) used in Sample 1 was replaced by the photographic coupler according to the present invention (the amount of addition was the same as that of the comparative coupler (a)). Samples 2 to 11 of the present invention were prepared. Hardening agents, activators and fungicides (mixtures of 2-methylisothiazol-3-one and 5-chloro-2-methylisothiazol-3-one) were added to each sample.

Each of the samples 1 to 11 obtained above was subjected to a wedge exposure according to a conventional method, and then subjected to a development process in the following step.

The processing conditions are as follows.

Processing Step Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching Fix 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds [Color developing solution] Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5.0 g Potassium bromide 0.02 g Potassium chloride 2.0 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g 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'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to make the total volume 1 l, and the pH is adjusted to 10.10.

[Bleaching-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 the pH to 5.7 with potassium carbonate or 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-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 Fluorescent brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g And adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The concentration of each of the samples 1 to 8 processed as described above was measured using a densitometer (model KD-7 manufactured by Konica Corporation).
(C, 80% RH) atmosphere for 14 days to examine the heat resistance and moisture resistance of the dye image. The results are shown below. However, heat resistance
The wettability is represented by the percentage of the dye remaining 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 resistance of the dye image was examined from the dye remaining rate after the light resistance test with respect to the initial density of 1.0. The results are shown below.

Dye Residual Rate (%) Sample No. Coupler Heat / moisture resistance / light resistance 1 Comparison (a) 87 41 2 Invention (I-2) 90 61 3 Invention (I-3) 88 604 Invention (I-4) 92 595 Invention ( I-7) 87 55 6 The present invention (II-1) 89 56 7 The present invention (II-11) 88 588 The present invention (II-14) 91 60 As is clear from the above results, the coupler of the present invention was Compared to the sample using the comparative coupler, the sample used had significantly improved light fastness and excellent heat and humidity resistance, indicating that a robust dye image was formed.

Example 2 The following layers were sequentially coated on a subbed triacetyl cellulose film support from the support side, and a green light-sensitive color reversal light-sensitive material containing the following couplers (Samples 9 to 14) )created.

First layer: emulsion layer 1.4 g of gelatin, green-sensitive silver chlorobromide emulsion (96 mol% of silver chloride)
A green sensitive emulsion layer consisting of 7.5 × 10 ^-4 mol of the following coupler dissolved in 0.5 g of dibutyl phthalate and 1.8 g of dibutyl phthalate.

Second layer: protective layer A protective layer containing 0.5 g of gelatin. In addition, 2,4-dichloro-6-hydroxy-s-triazine sodium salt was added as a hardening agent so as to be 0.017 g per 1 g of gelatin.

Each of the samples obtained above was subjected to wedge exposure according to a conventional method, and then subjected to development processing in the next step.

[Reversal processing step] Processing step Temperature Time First development 38 ° C for 6 minutes Washing 38 ° C for 2 minutes Inversion 38 ° C for 2 minutes Color development 38 ° C for 6 minutes Adjustment 38 ° C for 2 minutes Bleaching 38 ° C for 6 minutes Arrive 38 ° C for 4 minutes Rinse with water 38 ° C for 4 minutes Stable Room temperature 1 minute Drying Use the following composition for the treatment solution.

[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 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water 1000 ml [Inverting solution] Nitrilotrimethylenephosphonic acid hexasodium salt 3.0 g Stannous chloride (dihydrate) 1.0 g p-Aminophenol 0.1 g Sodium hydroxide 5.0 g Glacial acetic acid 15 ml Add water 1000 ml [Color developing solution] Sodium tetrapolyphosphate 2.0 g Sodium sulfite 7.0 g Sodium tertiary phosphate (12-hydrate) 36.0 g Potassium bromide 1.0 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-ethyl-N-β-methanesulfonamidoethyl -3-Methyl-4-aminoaniline / sulfate 11.0 g Ethylenediamine 3.0 g Add water 1000 ml [Adjustment solution] Sodium sulfite 12.0 g Sodium ethylenediaminetetraacetate (dihydrate) 8.0 g Thioglycerin 0.4 ml Glacial acetic acid 3 ml Water 1000 ml [Bleach] Sodium ethylenediaminetetraacetate (dihydrate) 2.0 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120.0 g Potassium bromide 100.0 g Add water to 1000 ml [fixed solution] Ammonium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Add water 1000 ml [Stabilized solution] Formalin (37% by weight) 5 ml Conidax (Konica Corporation) 5 ml Add water 1000 ml Samples treated as above , The light resistance, heat resistance and moisture resistance of the dye image were examined in the same manner as in Example 1. The results are shown below.

Dye Residual Rate (%) Coupler used Heat / 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 clear from the above, all of the samples using the coupler of the present invention have a higher dye residual ratio than the samples using the comparative coupler. It can be seen that they are excellent in heat and humidity resistance and light resistance and are robust.

Example 3 On a transparent polyethylene terephthalate film support,
The photothermographic layer comprising a support 1 m ² per following components was coated to create a photothermographic material.

Silver benztriazole 0.6 g gelatin 3.0 g reducing agent * 1 0.97 g coupler (II-12) of the present invention 1.0 g silver iodobromide (in terms of silver) 0.45 g polyvinylpyrrolidone 1.0 g benztriazole 0.02 g inhibitor * 2 0.001g Hot solvent * 3 4.5g

[0074]

Embedded image

After imagewise exposure of the above photosensitive material, it was superposed on an image receiving material obtained by coating polyvinyl chloride on photographic baryta paper and thermally developed at 150 ° C. for 1 minute. A cyan transfer image was obtained.

[0076]

The photographic coupler according to the present invention can be used as a material for a silver halide color photographic light-sensitive material, and an excellent color image free from a change in hue due to heat, moisture and light can be obtained. It is also effective as a dye-providing substance for photothermographic materials.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-224376 (JP, A) JP-A-63-280247 (JP, A) JP-A-63-281161 (JP, A) 505249 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 7/38

Claims (2)

(57) [Claims] 1. A photographic coupler represented by the general formula [I]. Embedded image [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 Rs may be the same or different. R ₁ represents a hydrogen atom or a substituent; X represents a hydrogen atom or a group which is eliminated by a reaction with an oxidized form of a color developing agent. ] 2. A photographic coupler represented by the general formula [II]. Embedded image [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 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 a reaction with an oxidized form of a color developing agent. ]