JPH0345819B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a method of forming a positive image by heat-developable color diffusion transfer and a photosensitive material, and more particularly, the present invention relates to a method of forming a positive image by heat-developable color diffusion transfer and a photosensitive material. The present invention relates to a method for forming a positive image by heat-developable color diffusion transfer, thereby obtaining a positive color image, and a heat-developable color photosensitive material suitable for use in the method. [Prior Art] The conventionally known color photography method using photosensitive silver halide is superior to other color photography methods in terms of photosensitivity, tonality, image preservation, etc., and is the most widely used color photography method. has been transformed into However, since this method uses wet processing for steps such as development, bleaching, fixing, and washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may pose a threat to the human body, or There are many problems, such as concerns about contamination of the room and workers by processing chemicals, and the labor and cost of waste liquid treatment. Therefore, there has been a demand for the development of a method for forming color images that allows dry processing. Black and white heat-developable photosensitive materials characterized by heat treatment in the development process have been known for a long time, and are described in, for example, Japanese Patent Publication No. 43-4921 and No. 43-4924. A photosensitive material comprising silver and a developer is disclosed. Furthermore, many color heat-developable photosensitive materials are also known, to which this black-and-white photothermographic material is applied. For example, US Patent No. 3531286, US Patent No. 3761270,
No. 3764328, Research Disclosure (hereinafter referred to as RD) No.
No. 15108, No. 15127, No. 12044, No. 16479, etc. are U.S. patents for heat-developable photosensitive materials containing photographic couplers and color developing agents.
No. 3180731, RD No. 13443 and RD No. 13437, etc.
U.S. Patent No. 1 for products using leuco dyes
No. 4235957, RD No. 14433, RD No. 14448, RD No.
15227, No. 15776, No. 18137, and No. 19419, etc., which apply the silver dye bleaching method, are disclosed in U.S. Patent Nos. 4124398, 4124387, and
No. 4123273 describes a method for thermally bleaching photothermographic materials. Furthermore, the diffusible dye is released by heat development,
JP-A-57-179840 and JP-A No. 57-57 disclose heat-developable color photosensitive materials in which a color image is obtained by separating the silver image and the dye by transferring this dye to an image-receiving layer.
-Described in No. 186744. Furthermore, Japanese Patent Application No. 122596/1983 filed by the present applicant proposes a method in which a sublimable dye is released by heat development and transferred to an image-receiving layer. Among these, methods that apply the above-mentioned silver dye bleaching method are known as methods that give positive images, and methods such as those described in the specification of Japanese Patent Application No. 164903/1983 filed by the present applicant are known. There is a process using a dye developer. However, in the method applying the silver dye bleaching method, it is necessary to perform silver dye bleaching treatment after heat development. It requires quite complex processing, such as processing with a lacquer and then transferring the dye. Another disadvantage is that there is a lot of contamination due to transfer of decomposed products to the image-receiving layer. On the other hand, said
The method using Dye-Dev has drawbacks such as not having very high discrimination between image and non-image areas, and also having low transferability of the dye itself. [Object of the Invention] Therefore, the object of the present invention is to provide a thermal development method that can obtain a positive image with high discrimination between image and non-image areas and high transfer density through a simple process of thermal development. The object of the present invention is to provide a method for forming a positive image by development color diffusion transfer, and a heat-developable color photosensitive material suitable for use in the method. Another object of the present invention is to prevent contamination (fogging) on the image receiving layer.
It is an object of the present invention to provide a method for forming a positive image and a positive type heat-developable color photosensitive material, which allows a positive thermal transfer dye image to be obtained without causing the occurrence of color. [Summary of the Invention] A method for forming a positive image by heat-developable color diffusion transfer according to the present invention that achieves the above object involves coupling a heat-diffusion transferable dye and an oxidized form of a reducing agent to a coupling reaction by heat development. It is characterized in that a positive image is obtained by producing a heat non-diffusion transferable and/or colorless substance and diffusing and transferring a heat-diffusion transferable dye that does not take part in the reaction to the image-receiving layer. In addition, the positive heat-developable color photosensitive material according to the present invention that achieves the above object includes (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, (d ) A heat-developable color photosensitive material having at least one photographic constituent layer containing a heat-diffusion transferable dye and (e) a binder, in which the heat-diffusion-transferable dye is converted into an oxidized form of the reducing agent by heat development. It is characterized by being a dye that generates a thermally non-diffusion transferable and/or colorless substance through a coupling reaction. [Structure of the Invention] One of the preferred embodiments of the present invention is that in the above-mentioned positive image forming method and photosensitive material according to the present invention, a heat diffusion transferable dye undergoes a coupling reaction with an oxidized product of a reducing agent by heat development. In the case of a dye that produces a heat non-diffusion transferable material by processing, the dye is a hydrophobic dye, and the reducing agent is a reducing agent having a hydrophilic group, and the hydrophobic dye is a reducing agent having a hydrophilic group. and is configured to generate a hydrophilic substance through a coupling reaction with the oxidized form of the reducing agent containing the hydrophilic group,
Moreover, a hydrophobic polymer is used as the image-receiving layer. At this time, both hydrophobic and hydrophilic binders can be used,
Preferably, a hydrophilic binder is used. That is,
This is a technique for obtaining a positive image by heat development using a heat diffusion transferable dye that loses its hydrophobicity through a coupling reaction with an oxidized form of a reducing agent having a hydrophilic group. On the other hand, in the positive image forming method and light-sensitive material according to the present invention, when the thermal diffusion transferable dye is a dye that produces a colorless substance by a coupling reaction with an oxidized form of a reducing agent during thermal development, The dye does not need to be hydrophobic or hydrophilic as long as it has thermal diffusion transferability. Further, the reducing agent does not need to contain a hydrophilic group and does not need to contain a hydrophobic group, as long as it can produce a colorless substance by reacting its oxidized form with the heat-diffusion transferable dye during heat development. It is also not necessary to contain groups.
Furthermore, there are no particular limitations on the image-receiving layer, and any binder may be used as long as it does not interfere with the thermal diffusion transfer of the thermal diffusion transferable dye. however,
The binder is preferably one that promotes diffusion transfer of the heat diffusion transferable dye during thermal development. The present invention will be described in detail below, but first, the case where a hydrophobic dye is used as the thermal diffusion transferable dye used in the present invention will be mainly described. In the present invention, the hydrophobic dye is coupled with the oxidized form of the reducing agent of the present invention to produce a hydrophilic and/or substantially colorless substance. As the hydrophobic dye used here, dyes represented by the following general formulas () and () are preferable. General formula () A-N=N-B General formula () A'-L-Dye In the formula, A and A' represent hydrophobic coupler residues, and B represents a substituted or unsubstituted aromatic group or a heterocycle. represents a group. In the general formula (), B is bonded to the coupler residue of A via an -N=N- bond through the active site of the coupler. Further, Dye represents a hydrophobic dye residue, and L represents a simple bond or a divalent organic group. In the general formula (), Dye does not necessarily need to be bonded to the active site of A' through L.
Also, when L is bound to the active site of A', -L
-Dye is limited to bonds that produce a substance or dye having a hydrophilic group when a reducing agent having a hydrophilic group and the hydrophobic dye undergo oxidative coupling. Examples of these groups include -OCODye, -OSO ₂ Dye,
−OSO ₂ NH−Dye, −OCONHDye, −
Examples include NHSO ₂ Dye group. The coupler residues denoted by A and A' are:
Active methylene compounds well known in the art,
Examples include phenol compounds or naphthol compounds, among which phenol, naphthol, pyrazolone, pyrazoloimidazole, pyrazolotriazole, and other open-chain ketomethylene compounds such as benzoylacetanilide, pivalylacetanilide, cyanoacetyl compounds, acetylacetone, etc. . The aromatic group or heterocyclic group represented by B includes a substituted or unsubstituted phenyl group, a naphthyl group,
Examples include pyridyl group. The hydrophobic dye represented by the general formula () reacts with an oxidized form of a reducing agent (CD) having a hydrophilic group as shown below (taking the case where the coupler residue is naphthol as an example). On the other hand, the hydrophobic dye represented by the general formula () reacts as follows. As described above, the hydrophobic dye of the present invention has hydrophilic and/or
or produce a substantially colorless substance. In the present invention, when an organic polymer or the like is used as the image-receiving layer, the dye having a hydrophilic group does not dye the organic polymer image-receiving layer, and only the remaining hydrophobic dye is dyed and transferred to the image-receiving layer. Therefore, a positive color image that is inversely proportional to the silver image is obtained. In the present invention, the coupler residues represented by A and A' undergo a coupling reaction with the oxidized color developing agent produced by thermal development, and are preferably represented by the following general formulas () to (). Examples include compounds that General formula () General formula () General formula () General formula () General formula () General formula () In the formula, R ¹ , R ² , R ³ and R ⁶ are preferably a halogen atom, (more preferably a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (preferably an alkyl group having 3 or less carbon atoms or an alkyl group having 3 or less carbon atoms). (substituted alkyl group), aryl group (preferably phenyl group),
an alkoxy group (preferably an alkoxy group having 3 or less carbon atoms), an amino group, an alkyl-substituted amino group (preferably an alkyl-substituted amino group in which the total number of carbon atoms in the alkyl group is 6 or less), a cyano group, or a nitro group, or a hydrogen atom, and further R ² and
R ³ may be bonded to form a 5- to 6-membered carbocycle or heterocycle (preferably a naphthol ring or quinosonol ring by condensation with a phenol ring), and R ⁴
represents an alkyl group (preferably an alkyl group having 3 or less carbon atoms) or an aryl group (preferably a phenyl group), R ⁵ represents an electron-withdrawing group (preferably a phenyl group), or -L- in the general formula () Represents dye. X is a group that can be separated from the coupler by a coupling reaction, and in the case of a dye represented by the general formula (), it is substituted with -N=N-B. In addition, among the dyes represented by the general formula (), if the dye is substituted at a site other than the active site of the coupler residue,
This is a group that is easy to couple with the oxidized form of the reducing agent (CD), such as a hydrogen atom or an active site substituent of a normal two-equivalent coupler. Hydrophobic substituents are preferred, especially halogen atoms, acyloxy groups,
Preferred are an alkoxy group, an aryloxy group, an arylthio group, and the like. On the other hand, in the case where a dye is bound to the active site of the coupler in general formula (), the active point binding group that connects the coupler residue and the dye moiety is oxidatively coupled to the reducing agent (CD) by the hydrophobic dye. Examples include the above-mentioned groups that sometimes produce substances having hydrophilic groups or pigments. Specific examples of coupler residues represented by A and A' that are preferably used in the present invention are as follows. The hydrophobic dye used in the present invention can be incorporated into the photographic constituent layer of the light-sensitive material by a known method. For example, dispersion can be carried out using a homogenizer or a fissure using a suitable solvent. The amount added is generally 0.1 to 10 per mole of organic silver salt.
mol, preferably 0.25 to 2 mol. Further, the photographic constituent layer containing the hydrophobic dye is
It may be a heat-developable photosensitive layer containing components (a), (b), (c), and (e), or it may be a layer adjacent thereto. The reducing agent (CD) having a hydrophilic group used in the present invention is preferably one having an aromatic amine-based hydrophilic group in the molecule, such as those described in Japanese Patent Application No. 57-225928. In particular, those having a sulfonic acid group or a carboxylic acid group are preferred. Examples are as follows. The reducing agent used in the present invention can be prepared using known methods such as Houben-Weyl, Methoden der Organis.
It can be synthesized according to the method described in Chen Chemie, Band/2, pages 645-703. These reducing agents can be used alone or in combination of two or more, and can also be used in combination with a black and white developing agent. The amount of reducing agent used depends on the type of organic silver salt used, the type of photosensitive silver halide, and the type of other additives, but it is usually 0.05 mol to 1 mol of organic acid silver salt.
The amount ranges from 10 mol, preferably from 0.1 mol to 3 mol. The heat-developable color photosensitive material of the present invention basically contains (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, (d) binder, and (e) thermal diffusion transferable dye in the same layer. However, the thermal diffusion transferable dye may be contained in a layer adjacent to the layer containing the other materials (a) to (d), etc.
It may be separated into the above layers. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method known in the photographic field, such as a single-jet method or a double-jet method, but in the present invention, a conventional silver halide gelatin emulsion preparation method is used. A light-sensitive silver halide emulsion prepared according to the method gives favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include gold sensitization, sulfur sensitization, gold-
Various methods such as sulfur sensitization and reduction sensitization can be used. The silver halide in the above-mentioned light-sensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.001 to about 1.5 μm, more preferably about 0.01 to about 0.5 μm. It is. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. Furthermore, as another method for preparing photosensitive silver halide,
It is also possible to cause a photosensitive silver salt-forming component to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method includes inorganic halides, such as
Halide represented by MXn (where M represents an H atom, _NH4 group or a metal atom, and X is
Cl, Br or I, n indicates the valence when M is an H atom or an NH ₄ group, and I when M is a metal atom.
Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, and lead. , antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium,
Examples include platinum and cerium. ), halogen-containing metal complexes (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-bromphthalimide, N-bromoacetamide,
N-iodosuccinimide, N-bromphthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo- 4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 to 1.0 per mol of organic silver salt.
mol, preferably 0.01 to 0.3 mol. Further, the heat-developable color photosensitive material of the present invention has a multilayer structure including each layer sensitive to blue light, green light, and red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. However, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used in each of these can be prepared by adding various spectral sensitizing dyes to the silver halide emulsion. You can get it. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine,
More preferred are those having a basic nucleus such as oxazole, thiazole, selenazole, and imidazole. Such nuclei include alkyl groups, alkylene groups, hydroxyalkyl groups, sulfoalkyl groups,
It may contain carboxyalkyl groups, aminoalkyl groups or enamine groups capable of forming fused carbocyclic or heterocyclic rings. Moreover, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat.
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these dyes added is 1.times.10.sup. ^-4 mol to 1 mol per mol of silver halide or silver halide-forming component. More preferably 1×10 ⁻⁴ mol to 1×10 ⁻¹
It is a mole. Examples of organic silver salts used in the heat-developable color photosensitive material of the present invention include Japanese Patent Publication No. 43-4924 and Japanese Patent Publication No. 44-4924;
No. 26582, No. 45-18416, No. 45-12700, No. 45
-22185 and JP-A-49-52626, JP-A No. 52-31728
No. 52-13731, No. 52-141222, No. 53-
No. 36224, Publications No. 53-37610, U.S. Patent No.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc., described in specifications such as No. 3330633 and No. 4168980, etc. Aromatic silver carboxylates such as silver benzoate, silver phthalate, etc., silver salts having an imino group such as silver benztriazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., silver salts of compounds having a mercapto group or a thione group, etc. 2-mercaptobenz-oxazole silver, mercaptooxadiazole silver,
Silver mercaptobenzithiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-phenyl-1,2,4-triazole, and also 4-hydroxy-6-methyl-1,3,3a,
Examples include silver 7-tetraza-indene and silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene. Further, silver compounds such as those described in RD16966, RD16907, British Patent No. 1590956, and British Patent No. 1590957 can also be used. Among these, silver salts having an imino group, such as silver benztriazole, are preferred. Examples of silver salts of benztriazole include alkyl-substituted silver benztriazole, such as silver methylbenztriazole, silver bromo-benztriazole, and silver chlorobenztriazole. Halogen-substituted benztriazole silver such as triazole silver, amide-substituted benztriazole silver such as 5-acetamidobenztriazole silver, and compounds described in British Patent Nos. 1590956 and 1590957, such as N-[6 -chloro-4-N(3,5-dichloro-4-hydroxyphenyl)imino-1-oxo-5-methyl-2,
5-Cyclohexadien-2-yl]-5-carbamoylbenztriazole silver salt, 2-benztriazol-5-ylazo-4-methoxy-1-
Naphthol silver salt, 1-benztriazole-5-
Examples include ylazo-2-naphthol silver salt, N-benztriazol-5-yl-4-(4-dimethylaminophenylazo(benzamide silver salt), etc. Also, nitrobenztriazoles represented by the following general formula () and benztriazoles represented by the following general formula () can be advantageously used.General formula () In the formula, R ₁₇ represents a nitro group, and R ₁₈ and R ₁₉ may be the same or different and each represents a halogen atom (e.g., chlorine, bromine, iodine), a hydroxy group, a sulfo group, or a salt thereof (e.g., sodium salt,
potassium salt, ammonium salt), carboxy group or its salt (e.g. sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or carbamoyl group, sulfamoyl group, alkyl group (which each may have a substituent) For example, methyl group, ethyl group, propyl group), alkoxy group (e.g. methoxy group, ethoxy group), aryl group (e.g. phenyl group) or amino group,
m represents an integer of 0 to 2, and n represents an integer of 0 to 1. Examples of substituents for the carbamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents for the sulfamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents include a carboxyl group and an ethoxycarbonyl group, examples of substituents for an aryl group include a sulfo group and a nitro group, and examples of substituents for an alkoxy group include a carboxy group, an ethoxycarbonyl group, and an amino group. Examples of the substituent include an acetyl group, a methanesulfonyl group, and a hydroxy group. The compound represented by the general formula () is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds. For example, 4-nitrobenzotriazole silver, 5
-Nitrobenzotriazole silver, 5-nitro-6
-chlorobenzotriazole silver, 5-nitro-6
-Methylbenzotriazole silver, 5-nitro-6
-methoxybenzotriazole silver, 5-nitro-
7-phenylbenzotriazole silver, 4-hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-7-nitrobenzotriazole silver, 4
-Hydroxy-5,7-dinitrobenzotriazole silver, 4-hydroxy-5-nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-
Nitro-6-methylbenzotriazole silver, 4-
Sulfo-6-nitrobenzotriazole silver, 4-
carboxy-6-nitrobenzotriazole silver,
5-Carboxy-6-nitrobenzotriazole silver, 4-carbamoyl-6-nitrobenzotriazole silver, 4-sulfamoyl-6-nitrobenzotriazole silver, 5-carboxymethyl-6-
Silver nitrobenzotriazole, Silver 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole, Silver 5-nitro-7-cyanobenzotriazole, Silver 5-amino-6-nitrobenzotriazole, Silver 5-nitro-7-(p-nitrophenyl) )
Benzotriazole silver, 5,7-dinitro-6-
Examples include silver methylbenzotriazole, silver 5,7-dinitro-6-chlorobenzotriazole, and silver 5,7-dinitro-6-methoxybenzotriazole. General formula () In the formula, R ₂₀ has a hydroxy group, a sulfo group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), or a substituent. _R21 represents a halogen atom (e.g., chlorine, bromine, iodine), a hydroxy group, a sulfo group, or a salt thereof (e.g., sodium salt, potassium salt). , ammonium salts), carboxy groups or salts thereof (e.g., sodium salts, potassium salts, ammonium salts), nitro groups, cyano groups, or alkyl groups that may each have substituents (e.g., methyl groups, ethyl groups, (propyl group), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group, ethoxy group), or amino group, p is 1 or 2, and q is an integer of 0 to 2. Further, examples of substituents for the carbamoyl group in R ₂₀ include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. can. Further, as a substituent for the alkyl group in R ₂₁ , for example, a carboxy group, an ethoxycarbonyl group, etc., as a substituent for an aryl group, for example, a sulfo group, a nitro group, etc., and as a substituent for an alkoxy group, for example, a carboxy group, an ethoxy group, etc. Examples of substituents for carbonyl groups and amino groups include acetyl groups, methanesulfonyl groups, and hydroxy groups. Specific examples of the organic silver salt represented by the general formula () include the following compounds. For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-hydroxybenzotriazole silver,
Silver sulfobenzotriazole, silver 5-sulfobenzotriazole, silver benzotriazole-4-sodium sulfonate, silver benzotriazole-5
- Sodium sulfonate, silver benzotriazole-4-potassium sulfonate, silver benzotriazole-5-potassium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, 4-
Silver carboxybenzotriazole, silver 5-carboxybenzotriazole, sodium benzotriazole-4-carboxylate, silver sodium benzotriazole-5-carboxylate, potassium silver benzotriazole-4-carboxylate, silver benzotriazole-5-carboxylic acid Potassium, silver benzotriazole-4-carboxylic acid ammonium, benzotriazole silver-5-carboxylic acid ammonium, 5-carbamoylbenzotriazole silver, 4
- Sulfamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy-7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4-hydroxy-7-sulfobenzotriazole Silver, 5,6-dicarboxybenzotriazole silver, 4,6-dihydroxybenzotriazole silver, 4-hydroxy-5-chlorobenzotriazole silver, 4-hydroxy-5-methylbenzotriazole silver, 4-hydroxy-5-methoxy Benzotriazole silver, 4-hydroxy-5
-Silver nitrobenzotriazole, silver 4-hydroxy-5-cyanobenzotriazole, silver 4-hydroxy-5-aminobenzotriazole, silver 4-hydroxy-5-acetamidobenzotriazole, silver 4-hydroxy-5-benzenesulfonamide benzotriazole silver, 4-hydroxy-5-
Hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxymethylbenzotriazole silver,
4-Hydroxy-5-ethoxycarbonylmethylbenzotriazole silver, 4-hydroxy-5-phenylbenzotriazole silver, 4-hydroxy-
5-(p-nitrophenyl)benzotriazole silver, 4-hydroxy-5-(p-sulfophenyl)
Benzotriazole silver, 4-sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5-methoxybenzotriazole silver, 4-sulfo-5-cyanobenzotriazole silver, 4- Sulfo-5-aminobenzotriazole silver, 4-sulfo-5-acetamidobenzotriazole silver, 4-sulfo-5
-benzenesulfonamidobenzotriazole silver, 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5 -Carboxymethylbenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-
Sulfo-5-phenylbenzotriazole silver, 4
-sulfo-5-(p-nitrophenyl)benzotriazole silver, 4-sulfo-5-(p-sulfophenyl)benzotriazole silver, 4-sulfo-5
-methoxy-6-chlorobenzotriazole silver,
4-Sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy-5-chlorobenzotriazole silver, 4-carboxy-5-methylbenzotriazole silver, 4-carboxy-5-
Nitrobenzotriazole silver, 4-carboxy-
5-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5-acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-
5-Carboxymethylbenzotriazole silver, 4
-Carboxy-5-phenylbenzotriazole silver, 4-carboxy-5-(p-nitrophenyl)
Examples include silver benzotriazole and silver 4-carboxy-5-methyl-7-sulfobenzotriazole. These compounds may be used alone or in combination of two or more. The method for preparing the organic silver salt according to the present invention is arbitrary, and the organic silver salt according to the present invention may be isolated and used by dispersing it in a binder by an appropriate means, or the organic silver salt according to the present invention may be used after being dispersed in a binder by an appropriate means. A silver salt may be prepared therein and used as is without isolation. The amount of organic silver salt used is 0.05 g per 1 m ² of support.
-10.0g, preferably 0.2g - 2.0g. In addition to the above-mentioned components, various additives may be added to the heat-developable color photosensitive material of the present invention, if necessary. For example, as a development accelerator, US Pat.
Alkali release agents described in the specifications of No. 3220846, No. 3531285, No. 4012260, No. 4060420, No. 4088496, No. 4207392, or RD15733, No. 15734, No. 15776, etc.; −12700, −CO as described in U.S. Pat. No. 3,667,959
Non-aqueous polar solvent compound having −, −SO ₂ −, −SO− groups, melt former described in U.S. Pat. No. 3,438,776, U.S. Pat. No. 3,666,477, JP-A-19525
There are polyalkylene glycols described in No. In addition, as a color toning agent, for example, JP-A-46-4928
No. 46-6077, No. 49-5019, No. 49-5020
No. 49-91215, No. 49-107727, No. 50-
No. 2524, No. 50-67132, No. 50-67641, No. 50-
No. 114217, No. 52-33722, No. 52-99813, No. 53
−1020, No. 53-55115, No. 53-76020, No. 53
−125014, No. 54-156523, No. 54-156524,
No. 54-156525, No. 54-156526, No. 55-4060
No. 55-4061, No. 55-32015, and West German Patent No. 2140406, West German Patent No. 2147063, West German Patent No.
2220618, U.S. Patent No. 3080254, U.S. Patent No. 3847612
No. 3782941, No. 3994732, No. 3994732, No. 3782941, No. 3994732, No.
Phthalazinone, phthalicide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, which are compounds described in the specifications of No. 4123282, No. 4201582, etc. , 2,3-dihydro-1,3-oxazine-
2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3
-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and mixtures of one or more of these with imidazole compounds Also, a mixture of at least one acid or acid anhydride such as phthalic acid or naphthalic acid and a phthalazine compound,
Further examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, Patent Application No. 57-73215, 57
-3-amino-5 described in specification No. 76838
-Mercapto-1,2,4-triazoles, 3
-acylamino-5-mercapto-1,2,4-
Triazoles are also effective. In addition, as anti-capri agents, for example, Japanese Patent Publication No. 11113/1983, Japanese Patent Publication No. 90118/1972, Japanese Patent Publication No. 49-90118,
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen Acetamide, N-
halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.),
Or sulfur-containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthion, polysulfide compounds, etc.), others, oxazoline, 1,2,4-triazole, Examples include compounds such as phthalimide. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45228, No. 50-119624, No. 50-120328, No. 45228, No. 50-119624, No. 50-120328, No.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-promo-2-tolylacetamide, 2-promo-2-tolylsulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tripromomethyl)-
Examples include 6-methyltriazine. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be performed using a sulfur-containing compound as described in Japanese Patent No. 50-77034. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium-based stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103, and U.S. Pat.
It may contain the activator stabilizer precursor described in No. 4060420. In addition to the above-mentioned components, the heat-developable color photosensitive material of the present invention may further include a spectral sensitizing agent, an antihalation dye, a fluorescent sensitizer, a hardening agent, an antistatic agent, a plasticizer, a spreading agent, etc. Various additives, coating aids, etc. are added. In the heat-developable color photosensitive material of the present invention, a hydrophilic binder and/or a hydrophobic binder can be used as the binder. The hydrophilic binder in the present invention refers to one that is soluble in water or a mixture of water and an organic solvent. Examples include proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, and useful polymers such as polyvinyl acetals (preferably with a degree of acetalization below 20%, e.g. polyvinyl butyral). , polyacrylamide, polyvinylpyrrolidone, ethylcellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), etc., but are not limited to these. If necessary, two or more types may be used in combination. The amount of binder is 1/10 to 10, preferably 1/10 by weight, per 1 part of organic silver salt for each photosensitive layer.
4 to 4 parts. Hydrophobic binders include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene styrene polymer, vinyl Examples include chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzylcellulose, cellulose acetate, cellulose propionate, and cellulose acetate phthalate. 2 again if necessary
A mixture of two or more species may be used. The amount of binder is 1/10 by weight per 1 part of organic silver salt for each photosensitive layer.
~10 parts, preferably 1/4 to 4 parts. Note that, if necessary, a hydrophilic binder and a hydrophobic binder may be used in combination. The layers containing the above components and other layers according to the present invention can be coated on a wide variety of supports. Examples of the support used in the present invention include plastic films such as cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyethylene film, polyethylene terephthalate film, and polycarbonate film, as well as glass, paper, and metals such as aluminum. Also baryta paper, resin coated paper,
Waterproof paper can also be used. In addition to the photosensitive layer, the heat-developable color photosensitive material of the present invention can be provided with various layers such as an overcoat polymer layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer depending on the purpose. The heat-developable color photosensitive material can form a dye image through imagewise exposure and heat treatment, but
For example, as in JP-A No. 56-130745, water is supplied or NH ₄ Fe (SO ₄ ) _{2.12H 2} O or Na ₃ PO ₄ .
Images may be formed by heat treatment in the presence of water-releasing compounds such as 12H ₂ O and the like. The transfer of a dye image to the image receiving layer depends on whether the transferable dye is hydrophilic or hydrophobic, but may be carried out using a solvent such as methanol, water, etc., or by heat-melting such as methyl anisate. Thermal transfer can be carried out by incorporating microcapsules of a thermal solvent such as the one described in JP-A-58-174949, or a thermal solvent such as that described in JP-A-58-174949. It is also possible to use a thermal transfer method as described in British Patent No. 1590957. The photosensitive material according to the present invention is imagewise exposed and then thermally developed to generate an imagewise distribution of a thermal diffusion transferable dye or a thermal diffusion transferable dye precursor. When applied to a color thermal diffusion transfer method in which at least a part of the imagewise distribution is thermally transferred to an image-receiving layer in a stacked relationship with a photothermographic material, the image density formed on the image-receiving layer is improved. gives a positive image. When the heat-diffusion transferable dye used in the present invention is a hydrophobic dye, various organic polymeric substances can be used for the image-receiving layer that can receive the dye. The following heat-resistant organic polymeric substances are preferred and may be used in the form of a film or coated on a suitable support. The mechanism by which the hydrophilic dye produced from the hydrophobic dye of the present invention enters the image-receiving layer made of these organic polymers is not necessarily clear, but at processing temperatures above the glass transition point, the heat of the polymer chains It is thought that the movement increases, and the dye enters the gaps between chain molecules that result. Examples of organic polymer substances used in the present invention include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives with substituents having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene,
Polyacetals such as polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polyfluorinated ethylene trichloride, polyacrylonitrile, poly-N,N-dimethylallylamide , polyacrylate with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group, polyacrylchloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly Polyesters such as tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polysulfone, bisphenol A
Mention may be made of polycarbonate, polycarbonates, polyanhydrides, polyamides and cellulose acetates. Even if these polymeric substances are used alone,
Moreover, a plurality or more may be combined and used as a copolymer. For example, cellulose acetate films such as triacetate and diacetate, polyamide films made from combinations of heptamethylene diamine and terephthalic acid, fluorene propylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenyl Examples include polyester films, polyethylene terephthalate films, and polycarbonate films made of a combination of carboxylic acid, bis-p-carboxyphenoxybutane, and ethylene glycol.
These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-α-benzenesulfonic acid, etc. as a modifier is effective. Further, the image receiving layer may be formed from a single layer or may be formed from multiple layers. Furthermore, the image-receiving layer may have a portion or layer containing titanium white in or outside the image-receiving layer to form a white reflective layer. In addition, when the heat-diffusion transferable dye used in the present invention is a hydrophilic dye as described later, the above-mentioned image-receiving layer may contain a compound having a sulfo group, a carboxy group, a sulfamoyl group, etc. in the molecule. A layer containing a trapping mordant is used. As specific examples of the mordant, nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, and quaternary cationic compounds thereof are widely known. U.S. Patent No. 2548564, U.S. Patent No. 2484430, U.S. Patent No.
No. 3148061 and No. 3756814 disclose vinylpyridine polymers and vinylpyridinium cationic polymers. US Pat. No. 2,675,316 discloses the use of polymers containing dialkylamino groups as mordants. US Patent No.
No. 2882156 discloses aminoguanidine derivatives. U.S. Patent No. 3625694, U.S. Patent No. 3859096
British Patent No. 1277453 and British Patent No. 2011012 disclose mordants that can be crosslinked with gelatin and the like. U.S. Patent No. 3958995, U.S. Patent No. 2721852, U.S. Patent No.
No. 2798063 discloses an aqueous sol type mordant. Further, JP-A-50-61228 discloses a water-insoluble mordant. Other U.S. Patent No. 3709690;
No. 3788855, West German Patent Application (OLS) No.
No. 2843320, Japanese Patent Publication No. 53-30328, No. 52-155528
No. 53-125, No. 53-1024, No. 54-74430
No. 54-124726, U.S. Patent No. 55-22766, U.S. Patent No. 3642482, U.S. Patent No. 3488706, U.S. Patent No. 3557066,
No. 3271147, No. 3271148, Special Publication No. 1983-
No. 29418, No. 56-36414, No. 57-12139, RD
-12045 (1974) discloses various mordants.
Any of these can be used in the present invention. The mordant is preferably one that does not easily migrate within the image-receiving layer (element); for this purpose, it may be crosslinked with gelatin or the like as exemplified above, or a water-insoluble mordant may be applied using a mixture of water and an organic solvent. Various methods have been used, such as emulsification, dispersion, and coating from an aqueous sol or latex dispersion. In either case, a sheet coated with an image-receiving layer (hereinafter sometimes referred to as an image-receiving sheet).
The diffusion transferable dye is transferred by overlaying the heat-developable photosensitive layer with a layer coated with a heat-developable photosensitive layer (hereinafter sometimes referred to as a photosensitive sheet), or by overlaying the photosensitive sheet with an image-receiving sheet after heat development. A positive image is thereby formed on the image-receiving sheet. Further, a heat-developable photosensitive layer (hereinafter sometimes referred to as a photosensitive layer) and an image-receiving layer may be provided on the same support. As described above, in the present invention, various polymers for dye images can be used as mordants in the image-receiving layer, but the image-receiving layer may be a separate image-receiving element containing the image-receiving layer on a suitable support. Furthermore, the image-receiving layer may be integrated with the above-mentioned heat-developable color photosensitive material. If desired, an opacifying layer can be included in the element to reflect the desired degree of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. Used and known. The opacifying layer can contain various agents that provide the necessary reflection, such as titanium dioxide. Similar to the heat-developable photosensitive layer according to the present invention, the protective layer, intermediate layer, undercoat layer, back layer and other layers also include the following:
Prepare each coating solution and apply the dipping method, air knife method, curtain coating method or U.S. Patent No. 3681294.
A photosensitive material can be prepared by various coating methods such as the potpour coating method described in No. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. Various exposure means can be used for the heat-developable photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. The original drawing may be a line image such as a technical drawing, or a photographic image with steps. Furthermore, the printing from the original drawing may be done by contact printing. In addition, images projected by a video camera, etc., and image information sent from a television station can be sent directly to a CRT or via an FOT, and this image is formed on a heat-developable photosensitive material using a contact lens or a lens, and then printed. You can also attach it. Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means and display means in various devices. this
It is difficult to create an LED that effectively emits blue light. In this case, to play a color image,
It is sufficient to use LEDs that emit green, red, and infrared light, and to design layers that are sensitive to these lights to thermally diffuse and transfer yellow, magenta, and cyan dyes, respectively. That is, the green light-sensitive layer may contain a yellow dye, the red light-sensitive layer may contain a magenta dye, and the infrared light-sensitive layer may contain a cyan dye. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light receiving element such as a CCD, storing it in the memory of a computer, etc., and applying so-called image processing to process this information as necessary, this image information is reproduced on a CRT and used as an image-like light source. Alternatively, there is a method in which three types of LEDs are directly emitted for exposure based on the processed information. After exposure of the heat-developable color photosensitive material of the present invention, the obtained latent image is, for example, 0.3
The photosensitive material can be developed by heating the entire surface in 120 seconds to 120 seconds. As long as the temperature falls within the above range, both high and low temperatures can be used by increasing or shortening the heating time. Especially about
A range of 110°C to 200°C is useful, and the heating means are
It may be a hot plate, iron, hot roller or the like. The above-mentioned photosensitive layer and image-receiving layer may be formed on the same support, or may be formed on separate supports. The image-receiving layer can be peeled off from the photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the photosensitive layer and uniformly heat-developed. Further, after the heat-developable color light-sensitive material is subjected to imagewise exposure and uniform heat development, an image-receiving layer may be placed thereon and the dye may be transferred by heating at a temperature lower than the development temperature. A transfer solvent can also be used for transfer from the heat-developable photosensitive layer to the image-receiving layer. As the transfer solvent, a low boiling point solvent such as methanol, ethyl acetate, diisobutyl ketone, etc. and a high boiling point solvent such as tri-n-trisyl phosphate, tri-n-nonyl phosphate, di-n-butyl phthalate are used. In the case of a boiling point solvent, it can be emulsified in gelatin using a suitable emulsifier and added to the mordant layer. In another specific method, a layer of gelatin-dispersed titanium dioxide can be provided over a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and a reflective color image can be obtained by viewing the transferred color image from the transparent support side. Embodiments of the present invention are not limited to those described above, and in the positive image forming method and photosensitive material according to the present invention, the heat diffusion transferable dye undergoes a coupling reaction with the oxidized form of the reducing agent during heat development, thereby causing heat transfer. In the case of a dye that produces a diffusion transferable substance, contrary to the preferred embodiment described above, the dye is a hydrophilic dye, and the reducing agent does not have a hydrophilic group, or even if it does have a hydrophilic group, it cannot be oxidized. A reducing agent from which a hydrophilic group is eliminated during or after the coupling process, and configured such that the hydrophilic dye undergoes a coupling reaction with an oxidized form of the reducing agent by heat development to generate a hydrophobic substance; Moreover, a hydrophilic polymer is used as the image-receiving layer. At this time, it is preferable to use a hydrophobic binder as the binder. That is, this other embodiment is a technique for obtaining a positive image by heat development using a heat diffusion transferable dye that loses its hydrophilicity through a coupling reaction with an oxidized product of a reducing agent having a hydrophobic group. It is. These items will be explained below. The thermal diffusion transferable hydrophilic dye used in this case is a dye having a sulfo group, carboxyl group, sulfamoyl group, etc. in the molecule as a hydrophilic group.
The reducing agent is preferably a reducing agent that oxidatively couples with the dye in an oxidized state to form a hydrophobic dye and/or a colorless substance. Examples of thermal diffusion transferable hydrophilic dyes include those having a structure in which a coupler residue known in the photographic industry is bound to a hydrophobic dye residue and an active site substituent having a sulfo group, a carboxyl group, a sulfamoyl group, etc. A coupler having an active site substituent having a hydrophilic group such as a sulfo group, a carboxy group, a sulfamoyl group, or a group that forms a hydrophobic dye in collaboration with a coupler residue, or a group that forms a hydrophobic dye in collaboration with a coupler residue. There are couplers having active site substituents that form hydrophilic dyes, and specific examples include the compounds shown below. Examples of reducing agents that form a hydrophobic dye and/or colorless substance by oxidative coupling with the above dye in an oxidized state include those that do not have a hydrophilic dye, contrary to the embodiments described above, or Even if the hydrophilic group is present, the hydrophilic group is preferably removed during or after oxidative coupling. In particular, aromatic amine reducing agents such as those listed below are preferred.

【formula】 【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】 〔Example〕

Examples of the present invention are shown below, but the present invention is not limited thereto. Example 1 <Preparation of 4-hydroxybenzotriazole silver salt> 34.0 g of silver nitrate was dissolved in 450 ml of water, and aqueous ammonia was added dropwise to the solution while stirring. The dropping was stopped when the formed silver oxide was completely dissolved. The above ammoniacal silver nitrate solution was added to a solution of 27.5 g of 4-hydroxybenzotriazole (synthesized according to the method described in Japanese Patent Application No. 1065/1982) dissolved in 350 ml of ethanol and stirred. The reaction solution was filtered, washed with water and methanol, and dried to obtain 46.4 g of white crystals of 4-hydroxybenztriazole silver. 4-Hydroxybenzotriazole silver 7.26g
(3.0×10 ^-2 mol) water-soluble polyvinyl butyral
25% aqueous solution (Sekisui Chemical, Esletsu W-201)
24 ml, water 116 ml, and methanol 70 ml were added, and the mixture was pulverized and dispersed in an alumina ball mill to obtain a silver salt dispersion. Furthermore, apart from the above dispersion, dyes (1), (14), (19), and (27) of the exemplary compounds were each added 1×
10 ^-2 mol and a 25% by weight aqueous solution of water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd., ESLETSUKU W-201) 34
ml and 160 ml of water were stirred and mixed in an alumina ball mill to obtain a dispersion of each pigment. Next, 25 ml of the above silver salt dispersion and 25 ml of the above dye dispersion were mixed, and 1 ml of pentaerythritol was added.
g, 5 ml of a 25% aqueous solution of water-soluble polyvinyl butyral, 36 mg of silver iodide emulsion with an average grain size of 0.04 μm, and 0.42 g of the following reducing agent as required, and each was coated on photographic baryta paper. The coating was applied with a wire bar to a wet film thickness of 65 μm. For each sample obtained by drying the above coating,
An exposure of 30,000 CMS was given through the step wedge. On the other hand, an image receiving layer having the following composition was prepared.

[Table] The polyvinyl butyral layer used as the intermediate layer of the above image-receiving layer is made of water-soluble polyvinyl butyral 25
% aqueous solution (Eslec W-201, Sekisui Chemical) 24
ml, 116 ml of water and 70 ml of methanol were added, and the mixture was applied to a wet film thickness of 30 μm and dried. For the uppermost layer containing titanium oxide, an aqueous solution containing 24 ml of a 25% polyvinyl butyral solution (Eslec W-201, manufactured by Sekisui Chemical Co., Ltd.), 116 ml of water, and 500 g of titanium oxide was applied to a wet film thickness of 65 μm. The exposed coated surface and the coated surface of the image-receiving layer were brought into close contact and heated under pressure for 40 seconds with an iron having a surface temperature of 160° C., and a positive image was obtained on the image-receiving layer. The results obtained are shown in Table 1 below.

[Table] Example 2 Eslec W- used in Example 1
A sample was prepared and tested in the same manner as in Example 1, except that gelatin was used instead of 201 and 0.7 g of dimethylurea was used instead of pentaerythritol as a melt former. Example 1
Similar good positive images were obtained. The results are shown in Table 2 below.

[Table] As is clear from Examples 1 and 2 above, it can be seen that according to the present invention, good positive images can be obtained using a heat development system using a normal negative emulsion. Example 3 Silver benzotriazole 6.78g (3.0×10 ^-2 mol)
25% polyvinyl alcohol aqueous solution (manufactured by Kuraray)
PVA-105), 116 ml of water, and 70 ml of methanol were added and dispersed in a ball mill for 48 hours using an alumina ball to prepare a silver salt dispersion. In addition, apart from the above dispersion, 1 x 10 ^-2 mol of each of exemplary dyes (31) and (39), 34 ml of a 25% polyvinyl alcohol (same as above) aqueous solution, and 160 ml of water were added.
The solution consisting of was subjected to ball mill dispersion (48 hours). Next, 25 ml of the above silver salt dispersion and 25 ml of the above pigment dispersion were mixed, and 1 g of D-xylitol and 25 ml of the above pigment dispersion were mixed.
5 ml of 25% polyvinyl alcohol aqueous solution and 36 mg of silver iodide emulsion with an average grain size of 0.04 μm, and further as a reducing agent. 0.55 g was added and coated onto baryta paper using a wire bar to give a wet film thickness of 65 μm, giving samples No. 9 and 10, respectively. Separately, an image-receiving layer was prepared by coating baryta paper with a layer of a 2:1 mixture of mordant and gelatin having the following structure to a dry film thickness of 3 μm to prepare an image-receiving sheet. The photosensitive sheet was passed through a step wedge and exposed to 30,000 CMS for each sample. Next, a polyethylene terephthalate base was adhered to the exposed coated surface, and heat development was performed at 170° C. for 30 seconds using a heat development machine Developer Per Module Model 277 manufactured by 3M. Next, after removing the polyethylene terephthalate base, a water-soaked image receiving layer was layered and laminated using a Konishiroku laminator (SAKURA ID SYSTEM).
After thermal transfer at 120°C using LAMINATER IDC108), positive images were obtained when the image-receiving layer was peeled off. The results are shown in Table 3.

【table】

Claims (1)

[Scope of Claims] 1. A thermally non-diffusion transferable and/or colorless substance is produced by a coupling reaction between a thermally diffusion transferable dye and an oxidized form of a reducing agent through thermal development, and the reaction is free of A method for forming a positive image by heat-developable color diffusion transfer, characterized in that a positive image is obtained by diffusion-transferring a heat-developable color pigment to an image-receiving layer. 2. At least one layer of photographic composition on a support containing (a) photosensitive silver halide, (b) organic silver salt, (c) reducing agent, (d) thermal diffusion transferable dye, and (e) binder. In a heat-developable color photosensitive material having a layer, the heat-diffusion transferable dye generates a heat-non-diffusion transferable and/or colorless substance by a coupling reaction with an oxidized form of the reducing agent during heat development. A positive heat-developable color photosensitive material characterized by: