JPH0420177B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a heat-developable color photosensitive material containing a sulfohydrazone derivative as a reducing agent and an active site-substituted coupler that has an immobilizing group as an active site-substituted component and forms a diffusible dye. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns about pollution to the human body due to processing chemicals, and There are many problems, such as concerns about contamination of workers by the chemicals mentioned above, and consideration of pollution caused by waste liquid. Therefore, there has been a demand for the development of a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be performed by heat treatment have attracted attention as photosensitive materials that meet the above-mentioned requirements. Regarding such heat-developable photosensitive materials, for example, Japanese Patent Publication No. 4921-4921 and Japanese Patent Publication No. 43-43
This is described in Japanese Patent No. 4924, etc., and discloses a photosensitive material comprising an organic silver salt, silver halide, and a reducing agent. These technologies form a latent image by exposing a photosensitive silver salt such as silver halide to light, and use this latent image as a catalytic nucleus to initiate an oxidation-reduction reaction between the organic silver salt and a reducing agent during heating. A silver image is obtained by As organic silver salts used in such heat-developable photosensitive materials, in addition to the above-mentioned Japanese Patent Publications Nos. 43-4921 and 43-4924, Japanese Patent Publications Nos. 44-26582 and 45
−18416, No. 45-12700, No. 45-22185, JP-A-49-52626, No. 52-31728, No. 52-
No. 137321, No. 52-141222, No. 53-36224, No.
Publications such as No. 53-37610 and U.S. Patent No.
Silver salts of aliphatic carboxylic acids such as silver laurate, myristic acid, etc., as described in the specifications of No. 3330633, No. 3794496, No. 4105451, No. 4123274, No. 4168980, etc. Examples include silver, silver palmitate, silver stearate, silver arachidonate, silver behenate, and silver α-(1-phenyltetrazolethio)acetate. In addition to the above, silver salts used in heat-developable photosensitive materials include Japanese Patent Publications No. 44-26582, No. 45-12700, and No. 45-12700.
No. 45-18416, No. 45-22185, Japanese Patent Application Publication No. 1983-
No. 31728, Publication No. 52-137321, Patent Application No. 1987-1065
Silver salts of imino groups as described in No. 57-1066, etc., such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, silver 5-methoxybenzotriazole, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, imidazole silver, pyrazole silver, urazole silver, 1,
Examples include 2,4-triazole silver and 1H-tetrazole silver. There have also been attempts to obtain color images by using color developing agents and couplers in the heat-developable photosensitive materials. Regarding such technology, for example, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, and U.S. Pat. A photosensitive material consisting of the following is disclosed. These techniques form a latent image by exposing a photosensitive silver salt such as silver halide to light.
Using this latent image as a catalytic nucleus, a color image is obtained by the reaction between the coupler and the quinone diimine produced by an oxidation-reduction reaction between the organic silver salt and the aromatic primary amine developing agent upon heating. As aromatic primary amines used in such heat-developable photosensitive materials, in addition to the above-mentioned U.S. Pat. No. 3,531,286, U.S. Pat.
No. 4138265, British Patent No. 2018453, etc., as described in Japanese Patent Application Laid-Open No. 51-6016, and Research Disclosure No. 13742, No. 16979, and No. 17039. Derivatives of p-aminophenol and p-phenylenediamine, such as p-aminophenol, 2,6-dichloro-4-aminophenol, 2,6-dibromo-4-aminophenol, 2,6-diiodo-4
-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol,
or their salts such as hydrochloride and sulfate, and N,N-dimethyl-p-phenylenediamine,
N,N-diethyl-p-phenylenediamine, N
-ethyl-N-carboxymethyl-2-methyl-
p-phenylenediamine, 3-acetylamino-
4-aminodimethylaniline, N-ethyl-N-
β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-++ aminoaniline, N-ethyl-N-β-hydroxyethyl-3
-Methyl-4-aminoaniline, N-ethyl-N
-β-methoxyethyl-3-methyl-4-aminoaniline, or their hydrochloride, sulfate, p-
Examples include salts such as toluenesulfonate. These aromatic primary amine developing agents are used with couplers of phenols, naphthols, pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles, α-acylacetanilides, and anilines, and are used with cyan, magenta, magenta, and aniline couplers, respectively. It can develop a yellow color and form a color image. However, these aromatic primary amines are unstable as compounds and, for example, form oxidized products by air oxidation. ) has drawbacks such as extremely poor storage stability. Furthermore, during emulsion preparation, contact with silver ions often causes development. Therefore, it has been considered to use a developing agent having a sulfonamide group in place of the aromatic primary amine developing agent. Examples of such developing agents include derivatives of sulfonamide phenol or sulfonamide aniline, such as 2,6-dichloro-4-benzenesulfonamide phenol, 2, as described in Research Disclosure No. 15108 and 15127. ,6-dichloro-4-(N,N-
dimethylsulfamoylamino)phenol,
2,6-dichloro-4-(2-thiophenesulfonamido)phenol is mentioned. Although these developing agents have better stability than the above-mentioned aromatic primary amine developing agents, the dye-forming reaction with the coupler is slow, resulting in the formation of only a slight color image or no color image at all. It has drawbacks. Furthermore, the coupler, which forms a dye by coupling with the oxidized form of an aromatic primary amine developing agent (quinone diimine), is not immobilized and can move between layers unreacted. This causes color turbidity in photosensitive materials. [Object of the Invention] Therefore, an object of the present invention is to provide a heat-developable color photosensitive material which is stable without development occurring during emulsion preparation and which has good storage stability after coating and drying. Another object of the present invention is to provide a heat-developable color photosensitive material that can rapidly form cyan, magenta, and yellow color images. Another object of the present invention is to use a developing agent and a coupler that are substantially immobilized in a binder, thereby preventing color turbidity in the layered light-sensitive material and preventing contamination of the image-receiving layer. The purpose of the present invention is to provide a heat-developable color photosensitive material. Still another object of the present invention is to provide a heat-developable color photosensitive material using a water-soluble developing agent. [Structure of the Invention] As a result of various studies carried out by the present inventors, the above-mentioned purpose was achieved by (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, and (d) diffusion by heat development. In the heat-developable color photosensitive material, the reducing agent is a compound represented by the following general formula [], and This can be achieved by a heat-developable color photosensitive material in which the dye-providing substance is an active point-substituted coupler that has an immobilizing group as an active point-substituted component and forms a diffusible dye. I found it. General formula [] In the formula, R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms, halogen atoms (for example, chlorine, bromine, etc.), amino groups (for example, amino groups, dimethylamino groups, etc.), and alkoxy groups. (e.g. methoxy, ethoxy, etc.) or alkyl groups (e.g. methyl,
ethyl, trifluoromethyl, etc.), R ⁵ represents an alkyl group (e.g., methyl, ethyl, etc.), and M represents a hydrogen atom, an alkali metal atom (e.g., a lithium, sodium, potassium, etc. atom). ), an alkaline earth metal atom (e.g. beryllium, magnesium, calcium, etc.) or an optionally substituted ammonium group (e.g. ammonium, trimethylammonium, pyridinium, etc.), preferably a hydrogen atom, an alkali metal It represents an atom, and n represents the same number as the valence of M. In the present invention, it is preferable that the active point substitution coupler having an immobilizing group in the active point substitution component and forming a diffusible dye is a compound represented by the following general formula []. General formula [] In the formula, Coupler is a group from which one hydrogen atom is removed from the active site of the coupler, and A is a divalent group that connects Coupler and B-C. Coupler- The bond of A is a cleavable group, preferably -O-, -OCO-, _-OSO2- , -
Each group such as OCONH-, -S-, -NHSO ₂ -, -N=N-, nitrogen-containing heterocycle, B is a divalent organic group (e.g., each group such as alkylene, arylene, aralkylene, etc., preferably carbon number 8 or more groups), C is an immobilizing group (e.g., polymer chain, sulfo group, sulfoamino group, sulfinic acid, sulfenic acid, thiosulfonic acid, dithiosulfonic acid, hydroxysulfonyloxy group, hydroxysulfonylthio group, carboxy group) , sulfamoylic acid, imidic acid, carboxyimidic acid, hydrazonic acid, carbohydrazonic acid,
Hydroximic acid, carbohydroxymic acid, hydroxamic acid, carbohydroxamic acid, sulfinimidic acid, sulfonimidic acid, sulfinohydrazonic acid, sulfonohydrazonic acid, sulfinohydrazonic acid, sulfonohydrazonic acid, etc. are preferred. represents a sulfo group, a sulfamino group, a carboxy group, etc.). According to a preferred embodiment of the present invention, the Coupler component of the active site substitution coupler having an immobilizing group in the active site substitution component and forming an active dispersible dye has the following general formula [], [], [], [], [],
It is a group represented by [] or []. General formula [] In the formula, R ⁶ is an alkyl group, an acyl group, an aryl group, R ⁷ and R ⁸ are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyl group, a nitro group,
A sulfamoyl group, m represents an integer of 1 to 4. General formula [] General formula [] General formula [] In each formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom, a halogen atom, a nitro group, a carboxy group, an amino group, or an alkyl group which may each have a substituent. , an aryl group, an alkoxy group or an alkylamino group, or a carbamoyl group, an arylcarbamoyl group, an alkylamide group, an arylamide group, an alkylsulfonamide group, an arylsulfonamide group, an aryloxycarbonyl group or an alkyloxycarbonyl group. General formula [] General formula [] General formula [] In each formula, R ¹⁵ is a hydrogen atom or an alkyl group, alkenyl group, cycloalkyl group, terpenyl group, aryl group, or heterocyclic residue which each may have a substituent, and R ¹⁶ is a hydrogen atom or each has a substituent. an alkyl group, an aryl group, a heterocyclic residue, an acylamino group, or an arylamino group, which may have a hydrogen ^atom , a halogen atom, or an alkyl group, an alkoxy group, or an alkylamide group, each of which may have a substituent. , arylamide group, carbamoyl group or sulfamoyl group, R ¹⁸ is a hydrogen atom, a halogen atom, or an alkyl group which may each have a substituent, an aryl group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an alkyl amide group, arylamide group, alkylsulfonamide group or arylsulfonamide group; 1 represents an integer of 1 to 4; The heat-developable color photosensitive material according to the present invention comprises a sulfohydrazone derivative which is a reducing agent precursor according to the present invention, and an active site substituted coupler which has an immobilizing group as an active site substituted component and forms a diffusible dye. (hereinafter referred to as the active site substitution type coupler of the present invention), a heat-developable color photosensitive material having improved emulsion stability and storage stability of a raw photosensitive material was obtained. Also, when obtaining a color image,
It was possible to quickly obtain excellent cyan, magenta, and yellow images, and also to obtain clear color images with no color turbidity during multilayering. Furthermore, it has become easier to add it into a water-soluble binder. Typical specific examples of the reducing agent of the present invention are listed below. [Exemplary compounds] Typical specific examples of the active site substitution type coupler of the present invention are listed below. [Exemplary compounds] The reducing agent of the present invention used in the heat-developable color photosensitive material of the present invention may be used alone or in combination of two or more. The amount used depends on the type of silver salt oxidizing agent used, the type of photosensitive silver halide, and the types of other additives added as necessary, but usually organic silver salt (oxidizing agent) )1
It ranges from 0.05 mol to 10 mol, preferably from 0.1 mol to 3 mol. In the heat-developable color photosensitive material of the present invention, the active site substitution coupler of the present invention is immobilized in the binder of the layer containing the coupler;
During thermal development, the immobilizing group of the active site substitution component is cleaved by a coupling reaction with the oxidized form of the reducing agent, and the dye that has lost its immobilizing group becomes a diffusible compound, and the dye is deposited on the image-receiving layer. An image can be formed. On the other hand, unreacted couplers and active site substitution components cleaved from the active sites during thermal development are still immobilized in the binder and do not diffuse into the image-receiving layer as well as between the layers. The active point substitution type coupler of the present invention, which is a dye-donating substance used in the present invention, is preferably colorless or light-colored, and colorless is particularly preferred.
This is because they do not color the layer and do not impair effective sensitivity. The active point substitution type coupler of the present invention, which is the dye-donating substance used in the present invention, differs depending on the developing photosensitive composition, coating conditions, processing method, etc., but in general, the amount is 0.01 mol to 10 mol per 1 mol of the silver salt oxidizing agent. The amount is preferably 0.1 mol to 2.0 mol. In order to incorporate the active site substitution type coupler of the present invention into the heat-developable photosensitive layer of the heat-developable color photosensitive material or its adjacent layer, a high-boiling point It can be dissolved and contained in a solvent.
Furthermore, in the above-described dispersion method, the active point substitution coupler of the present invention can be dissolved and contained in the heat-developable photosensitive layer or a layer adjacent thereto by using a low-boiling point solvent in combination with the above-mentioned high-boiling point solvent, if necessary. Examples of the above-mentioned high boiling point solvents include di-n-butyl phthalate, tricresyl phosphate, di-octyl phthalate, n-nonylphenol, etc., and examples of low boiling point solvents include methyl acetate, butyl propionate, Known examples include cyclohexanol and diethylene glycol monoacetate. Even if these solvents are used alone,
The active point substitution coupler of the present invention dissolved in a solvent may be used in combination with anionic surfactants such as alkylbenzenesulfonic acids and alkylnautalenesulfonic acids and/or sorbitan monolaurates. It can be mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant, emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and added to a heat-developable photosensitive layer or the like. The above-mentioned high boiling point solvent is used in an amount that completely dissolves the active point substitution coupler of the present invention, but preferably in the range of 0.05 to 100 parts per part of the active point substitution coupler of the present invention. can. In order to incorporate the active site substitution type coupler of the present invention into the heat-developable photosensitive layer of the heat-developable color photosensitive material or a layer adjacent thereto, a Fischer dispersion method can also be used. The Fisher dispersion method refers to dissolving and dispersing the active site substitution type coupler of the present invention, which has a hydrophilic component and a hydrophobic component in the same molecule, in an aqueous alkaline solution. For this dissolution and dispersion, an organic solvent compatible with water may be used, heating, stirring (homogenizer, ultrasonic dispersion, etc.) may be used, or the aid of a surfactant may be used. As the alkali in the alkaline aqueous solution, an inorganic base or an organic base that is compatible with water can be used, and after dissolving and dispersing the coupler,
You can also adjust the pH. In this case, an organic or inorganic acid compatible with water can also be used as a pH adjuster. The surfactant as a dispersion aid may be an anionic or nonionic surfactant, but an anionic surfactant is preferred. Fitzshear dispersion is also called Agfaer dispersion and is patented in UK patent 455556.
No. 465823, No. 298979 and patent application No. 1983-
You can refer to the technical content described in No. 104901. It is preferable that the active site substitution type coupler of the present invention is dispersed in the hydrophilic binder described below using a hydrophilic binder as described above in the heat-developable photosensitive layer. In this way, there is no need for grinding using a pole mill or sand mill as in the conventional method, and the dye image can be finely and stably dispersed in the heat-developable photosensitive layer in a short time. Transfer density can also be improved. In addition, in the present invention, a hydrophilic binder can be used as a binder for the heat-developable photosensitive layer as described later, so when the heat-developable photosensitive layer is coated on a support, a non-organic solvent, that is, an aqueous solvent is used. In particular, when gelatin is used as one of the binders, its setting properties can be utilized.
Since it is non-polluting and does not necessarily require horizontal coating, the work process for manufacturing photosensitive materials is also simplified. Examples of the organic silver salt (oxidizing agent) used in the photosensitive material of the present invention include Japanese Patent Publication Nos. 43-4921 and 44-26582.
No. 45-18416, No. 45-12700, No. 45-
No. 22185, JP-A-49-52626, JP-A No. 52-31728,
No. 52-137321, No. 52-141222, No. 53-36224
No. 53-37610, as well as U.S. Patent No. 3330633, U.S. Patent No. 3794496, U.S. Patent No. 4105451,
Silver salts of aliphatic carboxylic acids as described in specifications such as No. 4123274 and No. 4168980,
For example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, α-(1-phenyltetrazolthio)
Silver aromatic carboxylates such as silver acetate, such as silver benzoate, silver phthalate, etc.,
No. 45-12700, No. 45-18416, No. 45-22185,
Japanese Patent Publications No. 52-31728 and No. 52-137321,
Silver salts of imino groups such as those described in the specifications of Japanese Patent Application Nos. 57-1065 and 57-1066, such as benzotriazole silver, 5-nitrobenzotriazole silver, 5-chlorobenzotriazole silver, 5-
Methoxybenzotriazole silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5
-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver,
Examples include 1,2,4-triazole silver, 1H-tetrazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc. In addition, 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver,
2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene silver, 5-methyl-7
-Hydroxy-1,2,3,4,6-pentazaindene silver and the like. Among the above organic silver salts (oxidizing agents), silver salts of imino groups are preferred, and silver salts of benzotriazole derivatives are particularly preferred. Examples of the photosensitive silver halide used in the photosensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Examples include silver chlorobromide, silver chlorobromoiodide, silver chloroiodide, silver iodobromide, or mixtures thereof. These can be used in combination of one or more types. Silver halide can be prepared by any method known in the photographic field, such as a single jet method or a double jet method. The photosensitive silver halide may be chemically sensitized by any method known in the photographic field. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The photosensitive silver halide prepared in advance in this manner can be added to form a component used in the present invention. If gelatin is used as one of the binders in the present invention, there is an advantage that such a sensitization method can be easily carried out. As another method of preparation, a photosensitive silver halide-forming component may coexist with the organic silver salt (oxidizing agent) to form photosensitive silver halide in a portion of the organic silver salt (oxidizing agent). The photosensitive silver halide forming component used in this preparation method is an inorganic halide, for example, a halide represented by MX ² l [(where M represents a hydrogen atom, an NH ₄ group and a metal atom, and X ² is Halogen atoms (Cl, Br and I
atom), l indicates 1 when M is a hydrogen atom or _NH4 , and indicates the valence when M is a metal atom. The metal atoms here include lithium, sodium, potassium,
Rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum,
indium, lanthanum, ruthenium, thallium,
germanium, tin, lead, antimony, bismuth,
Chromium, molybdenum, tungsten, manganese,
Rhenium, iron, cobalt, nickel, rhodium,
Examples include palladium, osmium, iridium, platinum, and cerium. ] ; Halogen-containing metal complex [e.g. K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ ,
(NH ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ ,
(NH ₄ ) ₃ RuCl ₆ , (NH ₄ ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr ₆
etc.], onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylphosphonium bromide) Like 4
halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-
2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalic acid imide, N-bromoacetamide, N-iodosuccinimide, N-
-Bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzelsulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin etc.); other halides (e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid,
2-bromoethanol, etc.). These photosensitive silver halide and photosensitive silver halide forming components can be used in combination in various methods, and the amount used is in the range of 0.001 mol to 4.0 mol per 1 mol of organic silver salt (oxidizing agent). Preferably it is 0.01 to 1.0 mol. Additives such as development accelerators used in the light-sensitive material of the present invention include dicarboxylic acids and phthalazine described in Japanese Patent Application No. 1983-93396;
Carboxylic acids and carbonamides containing thioether groups as described in Japanese Patent Application No. 57-1064, and mercapto groups as described in Japanese Patent Application Nos. 57-73215 and 57-76836. Examples include triazoles and polyhydroxy compounds described in Japanese Patent Application No. 57-82064. Components other than those mentioned above that can be used in the photographic constituent layers of the light-sensitive material according to the present invention include known spectral sensitizers, antihalation agents, non-mercury antifoggants, printout inhibitors, water release agents, water retention agents, etc. Various additives can be optionally added. As the spectral sensitizer, certain kinds of sensitizers that are effective for silver halide emulsions are used. Examples include cyanine, merocyanine, rhodacyanine, and styryl pigments. Binders used in the photosensitive material of the present invention include synthetic or natural polymeric substances such as polyvinylpyrrolidone, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, gelatin, and phthalated gelatin. These can be used alone or in combination of two or more. For example, a combination of gelatin or a derivative thereof and polyvinylpyrrolidone or polyvinyl alcohol is effective. Examples of the support used in the photosensitive material of the present invention include synthetic plastic films such as polyethylene film, cellulose acetate film, and polyethylene terephthalate film, and paper supports such as photographic base paper, printing paper, baryta paper, and resin coated paper. It will be done. The above-mentioned components are coated on these supports together with a binder and an appropriate solvent to form a heat-developable photosensitive layer. The thickness of this layer is 1 μm to 1000 μm after drying.
m, preferably 3 μm to 20 μm. Further, if necessary, multiple layers may be applied in a superimposed manner, an intermediate layer may be provided, and an undercoat layer or an overcoat layer may be formed. The light-sensitive material of the present invention prepared in this manner is subjected to imagewise exposure as it is, and then is normally heated at a temperature in the range of 80 DEG C. to 200 DEG C. for 1 to 60 seconds for color development. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be heated at 70°C to 180°C before exposure.
Preheating may be performed in the temperature range of °C. Light sources suitable for image exposure include tungsten lamps, fluorescent lamps, mercury lamps, iodine lamps, xenon lamps, CRT light sources, laser light sources, and the like. The image thus obtained can be obtained as a color image on the receiver element in any manner. For example, Research Disclosure No. 15108,
15127, e.g. acetamide, 1,10-decanediol, succinimide, as a solvent such as methanol or as a hot solvent.
1,6-hexanedicarboxylic acid, 1,8-ethylenenaphthalene, methyl anisate, benzophenone, methyl stearate, methoxynaphthalene,
A color image can be obtained on an image-receiving element such as a transfer paper by bringing it into close contact with an image-receiving element such as a transfer paper containing biphenyl or the like, and peeling it off after heating if necessary. Alternatively, US Pat. No. 4,123,273,
The method described in each specification such as No. 4124387, No. 4124398, etc. and Japanese Patent Application Laid-open No. 56-27132,
For example, by bringing a layer containing a bleach-fixing agent into close contact with each other and, if necessary, peeling it off after heating, silver and silver salts in the light-sensitive material layer can be removed and a remaining color image can be obtained. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, embodiments of the present invention are not limited thereto. Example 1 20g of 4-sulfobenzotriazole and 4g
of sodium hydroxide to alcohol/water = (1:1)
was dissolved in 300 ml of solution. 20 ml of a 5N silver nitrate aqueous solution was added dropwise to this solution. At this time, a 5N aqueous sodium hydroxide solution was added dropwise to maintain the pH at 7-8. After stirring for 1 hour, add water to make 400ml.
- A sulfobenzotriazole silver dispersion was prepared. 3.3 g of exemplified compound (5) of the active site substitution coupler of the present invention (hereinafter abbreviated as the present coupler), 1.6 ml of 1% di(2-ethylhexyl)-2-sulfosuccinic acid aqueous solution, 2.8 ml of water, and 2 ml of methanol. were mixed, further 4 ml of 1N aqueous sodium hydroxide solution was added, and then 17.5 ml of 8% gelatin aqueous solution was added. After neutralizing this dispersion with 8% citric acid, 30ml
A coupler dispersion was prepared. The above 4-sulfobenzotriazole silver dispersion 4
ml and 6 ml of the coupler dispersion, and after sequentially adding 730 mg of polyvinylpyrrolidone, 520 mg of pentaerythritol, 310 mg of dimethylurea, 3 ml of water, and 280 mg of exemplified compound (1) of the reducing agent of the present invention, the mixture was mixed with 8% citric acid. The pH was set to 5.5. This dispersion contains a silver bromide emulsion (1 kg of emulsion contains 60 g of gelatin and 0.35 mole of silver).
1 ml of a cubic emulsion with an average grain size of 0.06 μm was added. This coating solution was coated onto a polyethylene terephthalate base so that the amount of silver was 6 mg per 100 cm ² to prepare a photosensitive material (A). The following operations were also performed for comparison. A comparative light-sensitive material was prepared in exactly the same manner except that 220 mg of the following comparative compound [] was added in place of the exemplified compound (1) of the reducing agent of the present invention when adding each compound.
(B) was created. The photosensitive materials (A) and (B) prepared in this way are exposed to white light through a step wedge.
An exposure of 1600 CMS (candela meters seconds) was given. Next, it was stacked with image-receiving paper and heated at 160° C. for 30 seconds for development, and then the image-receiving paper was peeled off. The image receiving paper used here was a dry film thickness of 50μ using a 10% vinyl chloride solution in tetrahydrofuran on photographic baryta paper.
It was applied so that it became m. Further, the photosensitive material (A) and the photosensitive material (B) were left under forced deterioration conditions at a temperature of 50° C. and a relative temperature of 50% for 24 hours, and then exposed and developed in the same manner. The results obtained on the receiving paper are shown in Table 1. Comparative compound - []

[Table] The obtained magenta negative image was measured by reflection density against red light. Specific sensitivity is the sensitivity before deterioration as 100
It shows the relative sensitivity when As is clear from Table 1, the photosensitive material of the present invention
It can be seen that (A) has very good shelf life. Example 2 In Example 1, 300 mg of Exemplified Compound (3) was used in place of Exemplified Compound (1) of the reducing agent of the present invention, and 60 g of gelatin was used in 1 kg of emulsion as a silver bromide emulsion.
3,3'-di-(γ-sulfopropyl)-9-methyl-thiadicarbocyanine sodium salt was added to a cubic emulsion with an average grain size of 0.10 μm containing 0.35 mol of silver and 0.35 mol of silver.
A coating solution was prepared in the same manner as in Example 1, except that 1 ml of the emulsion containing 4×10 ^-10 mol/mol was added to the dispersion. This coating solution was coated onto a polyethylene terephthalate base so that the amount of silver was 6 mg per 100 cm ² to form a first layer. Next, an aqueous solution prepared by mixing 20 ml of a 6% gelatin aqueous solution and 50 ml of a 6% polyvinylpyrrolidone aqueous solution was applied onto the first layer to form an intermediate layer. Next, a coating liquid was prepared in the same manner as in Example 1 except for the following three points. When preparing a coupler dispersion liquid, exemplified compound (11) is used instead of exemplified compound (5) of the coupler of the present invention.
3.2g of was used. In place of exemplified compound-(1) of the reducing agent of the present invention, 300 mg of exemplified compound-(3) was used. As a silver bromide emulsion, 60 gelatin is contained in 1 kg of emulsion.
3,3'-di-(γ-sulfopropyl) in a cubic emulsion with an average grain size of 0.125 μm containing g and 0.35 moles of silver.
1 ml of an emulsion containing 4 x 10 ^-4 mol of -5,5'-diphenyl-9-ethylcarbocyanine sodium salt per mol of silver was used. This coating solution was applied onto the intermediate layer so that the amount of silver was 6 mg per 100 cm ² to form a second layer. A photosensitive material (C) was prepared by the above operations. Next, a comparative photosensitive material (D) was prepared in exactly the same manner as the photosensitive material (C) except for the following two points. When preparing the coupler dispersion liquid used in the first layer, instead of the exemplified compound of the coupler of the present invention (5), 2.5 g of the following comparative compound [] was added to 2.5 ml of dibutyl phthalate and ethyl acetate (hereinafter referred to as EA) 5
mixed in ml. Add to this solution 1 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and a 5% aqueous gelatin solution.
25 ml was added and emulsified using a colloid mill to prepare a coupler dispersion. When preparing the coupler dispersion used in the second layer, 2.5 g of the following comparative compound [] was mixed and dissolved in 2.5 ml of dibutyl phthalate and 5 ml of EA in place of the exemplary compound (11) of the coupler of the present invention. To this solution, 1 ml of a 10% aqueous solution of Alkanol B and 25 ml of a 5% aqueous gelatin solution were added and emulsified using a colloid mill to prepare a coupler dispersion. A comparison photosensitive material (D) was prepared by the above operations. The photosensitive materials (C) and (D) prepared in this way are exposed to white light through a step-up technique, respectively.
Exposure was given to 1600 CMS and red light and green light. Next, the image receiving paper (same as in Example 1) was placed on top of the image receiving paper and heated at 160° C. for 30 seconds, and after development, the image receiving paper was peeled off. As a result, from the photosensitive material (C), a red image was obtained in the white exposure area, a magenta image without color turbidity in the red exposure area, and a yellow image without color turbidity in the green exposure area. On the other hand, from the comparative light-sensitive material (D), a low-density, pale image with red to red in all of the white exposure area, red exposure area, and green exposure area was obtained. This shows that the photosensitive material (C) of the present invention does not cause color turbidity. On the other hand, in the comparative light-sensitive material (D), since the coupler does not have an immobilizing group, it is thought that interlayer migration occurred, resulting in color turbidity. Moreover, the magenta dye produced in the comparative light-sensitive material (D) had a large molecular weight, so it was difficult to dye the image-receiving layer, and the density was low.

Claims (1)

[Scope of Claims] 1 (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, (d) dye-donating substance that forms a diffusible dye upon thermal development, and (e) binder In the heat-developable color light-sensitive material having at least one photographic constituent layer containing 1. A heat-developable color photosensitive material, which is an active point substitution coupler which forms a diffusible dye. General formula [] (In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, a halogen atom, an amino group, an alkoxy group or an alkyl group, R ₅ represents an alkyl group, M is a hydrogen atom, an alkali metal atom, It represents an alkaline earth metal atom or an optionally substituted ammonium group, and n represents the same number as the valence of M.)