JPH0530259B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical field] The present invention relates to a new heat-developable color photosensitive material.
More specifically, it relates to a heat-developable color light-sensitive material that obtains an image by thermally transferring the imagewise distribution of diffusible dyes released or formed in the heat-developable color light-sensitive material (element) to an image-receiving element. The present invention relates to a heat-developable color photosensitive material that allows transfer images to be obtained on plain paper or the like without requiring an image-receiving element subjected to such processing. [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, in this method, wet processing is used for steps such as development, bleaching, fixing, and water washing, which takes time and effort, and there are concerns that the processing chemicals may cause pollution to the human body, or the processing room and There are many problems, such as concerns about contamination of workers by treatment chemicals, and furthermore, 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. Heat-developable black-and-white photosensitive materials characterized in that the development process is carried out by heat treatment have been known for a long time. A photosensitive material comprising silver oxide and a developer is disclosed. Furthermore, many heat-developable color photosensitive materials are also known, which are based on this heat-developable black-and-white photosensitive material. For example, US Patent No. 3531286, US Patent No. 3761270, US Patent No.
No. 3764328, Research Disclosure (hereinafter referred to as
(abbreviated as RD) No. 15108, No. 15127, No. 12004, and No. 16479, etc. are U.S. Patent No. 3180731 regarding photothermographic materials containing photographic couplers and color developing agents. , RDNo.13443 and the same
No. 14347, etc. include U.S. Patent No. 4235957, RD No. 14433, and U.S. Patent No. 14433 for those using leuco dyes.
14448, No. 15227, No. 15776, No. 18137, and No. 19419, etc., apply silver dye bleaching method, and US Pat. Thermal bleaching methods for heat-developable photosensitive materials are each described. However, these proposals regarding heat-developable color photosensitive materials are difficult or impossible to bleach or fix the simultaneously formed black, white, and silver images, or even if it is possible, wet processing etc. are not required. It is what you need. Therefore, these proposals have many drawbacks, such as difficulty in obtaining clear color images and the need for complicated post-processing. As a method to improve the above-mentioned drawbacks, a heat-developable color photosensitive material was published in Japanese Patent Application Laid-Open No. 57-179840, in which a color image is obtained by transferring the diffusible dye released by heat development.
No. 57-186744, No. 57-198458, No. 57-
No. 207250, No. 58-40551, No. 58-58543, and the present inventors' No. 59-
It is also shown in the specifications of Japanese Patent Application No. 12431 and Japanese Patent Application No. 57-229649. In these proposals, a dye-providing substance having a diffusible dye in the same molecule releases the diffusible dye through a heat development reaction of an organic silver salt, and transfers the diffusible dye to an image-receiving layer to obtain a color image. In this specification, this is referred to as a "dye-releasing type." On the other hand, Japanese Patent Application No. 57-229671 by the present inventors,
The proposal shown in the specifications of No. 58-33363 and No. 58-33364 is that a colorless or light-colored dye-donor substance reacts with an oxidized product of a color developing agent produced by a heat development reaction of an organic silver salt to generate heat. A color image is obtained by forming a diffusible dye and transferring it to an image-receiving layer, and is referred to herein as a "dye-forming type". Regardless of the dye-releasing type or dye-forming type, in a method in which the dye is diffusely transferred using heat and an image is formed by the transferred dye, there are various factors such as image density, image fixability, and image resistance to heat, light, humidity, etc. A specially processed image receiving sheet (image receiving element) is used for stability, image tone adjustment, etc. This image-receiving sheet has an image-receiving layer on a support, and the image-receiving layer only needs to have the function of receiving the dye released or formed by thermal development, and contains a mordant used in dye diffusion transfer type light-sensitive materials. and Japanese Patent Application Publication No. 1983
-The glass transition temperature described in No. 207250, etc. is 40℃
A material made of a heat-resistant organic polymer material having a temperature of 250° C. or less is preferably used. As specific examples of the mordant and heat-resistant organic polymer substance used in the image-receiving layer, compounds described in Japanese Patent Application No. 58-223274 are known. Recently, attempts have been made to form transferred images on so-called plain paper without using the above-mentioned specially processed image-receiving sheet, but conventional heat-developable color photosensitive materials suffer from deterioration in image density. It has been difficult to obtain stable images with sufficient density on plain paper, etc., resulting in deterioration of image fixability and stability. Therefore, there has been a demand for the development of a diffusion transfer type heat-developable color photosensitive material that can form a transferred image on plain paper or the like that has not undergone any special processing. [Object of the Invention] The object of the present invention is to provide a diffusion transfer type heat-developable color photosensitive material that can form transferred images while maintaining high transfer density and image stability even on paper that has not been specially processed. The purpose is to provide materials. [Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have discovered that at least a photosensitive silver halide, an organic silver salt, and a diffusible dye can be released or formed on a support by heat development. In a heat-developable color light-sensitive material having a photographic constituent layer containing a dye-providing substance, a reducing agent, and a binder, the outer layer of the photographic constituent layer is a heat-fusible layer containing a heat-fusible compound. The inventors have discovered that the above object can be achieved and have completed the present invention. That is, in the present invention, the heat-fusible substance contained in the heat-fusible layer is transferred to the image-receiving element together with the transfer of the diffusible dye during thermal development, and the heat-fusible substance promotes the dyeing of the dye to the image-receiving element. , or the heat-melting substance receives the dye by adsorption, dissolution, etc., and transfers the dye to an image-receiving element (for example, plain paper, etc.) whose surface has not been specially processed such as a dyed layer. be able to. Furthermore, the provision of a heat-fusible layer has the effect of increasing adhesion to the image-receiving element, increasing transfer density and improving releasability. The present invention will be specifically explained below. Generally, a heat-developable color photosensitive material consists of a photosensitive element and an image-receiving element, and by using both elements in combination, it is possible to obtain a color dye image on the image-receiving element. Of the two elements, the present invention is characterized by the photosensitive element, and therefore, as long as the photosensitive element of the present invention is used, it can be used in combination with a known image receiving element, such as plain paper that has not been specially processed. It is clear that the invention also falls within the technical scope of the present invention. The relationship between the photosensitive element and the image receiving element of the present invention may be in any conventionally known form, for example,
(1) With respect to the photosensitive element of the present invention, the image receiving elements are placed in a stacked relationship during thermal development; and (2) with respect to the photosensitive element of the present invention, upon thermal transfer after thermal development. (3) the image-receiving element is integrally provided on the photographic constituent layer of the photosensitive element of the present invention, and through the image-receiving element imagewise exposure, It may be in any format in which heat development is performed, or (a)
The image receiving element may be peeled off after thermal transfer, or (b) the image receiving element may not be peeled off after thermal transfer. In the present invention, any of the above-mentioned embodiments can be preferably applied as a mode of diffusion transfer using plain paper or the like that has not undergone any special processing as an image receiving element. The photosensitive element of the present invention is characterized in that it has a heat-fusible layer as an outer layer of the photographic constituent layers formed on the support. Here, the outer layer has the following meaning. [1]
In the case where the photosensitive element of the present invention is constructed separately from the image-receiving element [format (1) or (2) above], the layer farthest from the support is referred to as the outer layer, and [2] the photosensitive element of the present invention In the case of a type in which the layer is integrated with the image-receiving element [format (3) above], the layer on the boundary side with the image-receiving element is called an outer layer. In addition, if an opaque layer etc. is provided,
This layer is understood to be the layer on the image-receiving element side. In the configuration [1] above, a layer (protective layer, etc.) that does not inhibit the effects of the heat-fusible layer may be provided on the heat-fusible layer of the present invention, and furthermore, a layer (protective layer, etc.) may be provided on the heat-fusible layer of the present invention. The thermofusible layer may be composed of two or more layers. The same applies to the case [2] above. The heat-fusible layer is composed of a heat-fusible substance alone or a heat-fusible substance and a binder, and may further contain various additives. The heat-melting material of the present invention is substantially colorless or white, has good compatibility with the dye to be transferred, has good affinity with the image-receiving element, and is solid or semi-solid at room temperature. Preferably 30℃ or higher and 250℃
Substances that melt or soften when heated at temperatures below (more preferably 40°C or higher and 180°C or lower), such as higher fatty acid esters (e.g. ethyl stearate, ethyl behenate, etc.), waxes (e.g. carnauba wax, beeswax, etc.) ), amides (e.g. acetamide, acetanilide, octadecanamide, propionamide, etc.), alcohols (e.g. 1-octadecanol, 1-eicosanol,
1,12-dodecanediol, 1,6-hexanediol, etc.), amines (e.g. 4-dodecylaniline, octadecylamine, etc.), ureas (e.g. dimethylurea, diethylurea, diphenylurea, etc.), or polyethylene glycol, poly- It is a polymer such as 1,4-butylene adipate. These thermofusible materials are selected primarily depending on the nature of the dye being transferred and the nature of the receiving element. The content of the heat-melting substance in the present invention is 5% to 500%, preferably 10% of the amount of binder in the photosensitive layer.
~300%. Two or more of the heat-melting substances of the present invention may be used in combination, and they may be dissolved in an appropriate solvent and applied alone or together with an appropriate binder, or they may be applied without using a solvent by a hot-melt method or the like. can.
The thickness of the thermofusible layer formed by this method is
It is 0.01 μm to 500 μm, preferably 0.5 μm to 100 μm. The binder that may be used in the heat-fusible layer may be selected from hydrophilic binders and hydrophobic binders depending on the heat-fusible substance of the present invention, such as polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, Polyvinylpyrrolidone, polystyrene, styrene-butadiene copolymer, cellulose esters (ethyl cellulose, etc.), acrylic resin (methyl methacrylate, etc.), gelatin, etc. can be used. Further, the heat-melting substance can also serve as a binder. Various additives can be further added to the heat-fusible layer of the present invention. Examples of additives include antioxidants, ultraviolet absorbers, and quenching substances.
In addition, if the diffusible dye released or formed from the dye-donating substance is a chelatable dye, metal ions that form a chelate with the dye (e.g., copper (),
Compounds containing nickel (), aluminum (), cadmium (), cobalt (), chromium (), etc.) may be added, in which case a stable chelate dye image is obtained in the receiving element. Further, the heat-fusible layer of the present invention may contain a substance that facilitates thermal peeling from the photographic constituent layers of the light-sensitive element. Next, the photographic constituent layers of the present invention will be explained. The photographic constituent layer has at least one heat-developable photosensitive layer, and may have two or more photosensitive layers having different color sensitivities as necessary, and may also include an undercoat layer, a backing layer, an intermediate layer, etc. It may have various layers such as a layer or a filter layer. The photosensitive layer basically includes photosensitive silver halide,
It contains the following components: an organic silver salt, a dye-providing substance, a reducing agent, and a binder, but it is not necessary that all the components be contained in one layer. For example, the dye-providing substance may be contained in a layer adjacent to a photosensitive layer containing other components, or separately contained in two or more layers so that each component can react. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures thereof. can give. 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 photosensitive emulsion may be coarse grains or fine grains, but the preferred grain size is about 0.001 μm to about 1.5 μm,
More preferably, it is about 0.01 μm to about 0.5 μm. The photosensitive silver halide emulsion prepared as described above can be most preferably applied to a heat-developable photosensitive layer. In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt to form photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example a halide represented by MXn (where M represents an H atom, NH ₄ group or a metal atom, and X represents Cl, Br or I, n is M is an H atom,
When it is an NH ₄ group, it is 1, and when M is a metal atom, it shows its valence. 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, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, Examples include cobalt, nickel, rhodium, palladium, osmium, iridium, 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. tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide), quaternary ammonium halides such as trimethylbenzylammonium bromide , quaternary phosphonium halides such as tetraethylphosphonium bromide, tertiary sulfonium halides such as benzylethylmethyl bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform, bromoform tetrabromide, etc.) carbon, 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 mol to 3.0 mol, preferably 0.01 mol to 1.0 mol, per 1 mol of organic silver salt. It is a mole. Further, the heat-developable photosensitive layer of the present invention may have 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 obtained by adding various spectral sensitizing dyes to the silver halide emulsion. can. 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 dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridineoxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups, hydroxyalkyl groups, sulfoalkyl groups,
It may contain a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. Further, 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, supersensitizing additives that do not absorb visible light such as ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as those described in the specifications of US Pat. No. 2,933,390 and US Pat. I can do it. 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 mole. As the organic silver salt used in the present invention,
No. 43-4924, No. 44-26582, No. 45-18416, No.
No. 45-12700, No. 45-22185, and JP-A No. 1973-
No. 52626, No. 52-31728, No. 52-13731, No. 52
Silver salts of aliphatic carboxylic acids described in the specifications of -141222, 53-36224, 53-37610, U.S. Patent No. 3330633, U.S. Patent No. 4168980, etc.
For example, silver laurate, silver myristate, silver valmitate, silver stearate, silver arachidonate, silver behenate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., and silver salts having an imino group. , for example silver salts of compounds having mercapto or thione groups, such as silver benzotriazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., for example silver 2-mercaptobenzo-oxazole, silver mercaptooxadiazole, silver mercaptobenzothiazole, 2- Mercaptobenzimidazole silver, 3-mercapto-phenyl-1,2,4-
Triazole silver, and also 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene silver, 5-methyl-7-hydroxy-1,
Examples include 2,3,4,6-pentazaindene silver. Also RD16966, RD16907, British Patent No. 1590956
It is also possible to use silver compounds such as those described in No. 1,590,957. Among these, silver salts having an imino group such as benzotriazole silver salts are preferred, and as benzotriazole silver salts,
Alkyl-substituted benzotriazole silver, e.g. methylbenzotriazole silver, e.g. bromo-
Halogen-substituted benzotriazole silver such as benzotriazole silver, chlorbenzotriazole silver, amide-substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and also described in British Patent No. 1590956 and British Patent No. 1590957. compounds, such as N-[6-chloro-4-
N(3,5-dichloro-4-hydroxyphenyl)
imino-1-oxo-5-methyl-2,5-cyclohexadien-2-yl]-5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1 -benzotriazol-5-ylazo-2-naphthol silver salt, N-benzotriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt, and the like. Further, nitrobenzotriazoles represented by the following general formula () and benzotriazoles represented by the following general formula () can be advantageously used. General formula () In the formula, R ¹ represents a nitro group, R ² and R ³ 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 is 0
~2, n represents 0 or 1. Further, examples of substituents for the carbamoyl group include a methyl group, ethyl group, acetyl group, etc., and examples of substituents for the sulfamoyl group include a methyl group, an ethyl group, an acetyl group, etc. Examples of substituents for alkyl groups include carboxy groups and ethoxycarbonyl groups; examples of substituents for aryl groups include sulfo groups and nitro groups; examples of substituents for alkoxy groups include carboxy groups and ethoxycarbonyl groups. and substituents for the amino group include, for example, 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-
Chlorbenzotriazole 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 ⁴ 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. ^R5 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 alkyl group which may have a substituent (e.g. methyl group, ethyl group, propyl group), aryl It represents a group (for example, phenyl group), an alkoxy group (for example, methoxy group, ethoxy group), or an 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 ⁴ include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. be able to. Furthermore, the above
Examples of the substituent for the alkyl group in R ⁵ include a carboxy group and an ethoxycarbonyl group; examples of the substituent for the aryl group include a sulfo group and a nitro group; and examples of the substituent for the alkoxy group include a carboxy group, Ethoxycarbonyl group, etc.
Examples of substituents for the amino group include an acetyl group, a methanesulfonyl group, and a hydroxy group. 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-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sodium sulfonate, benzotriazole silver-5-sodium sulfonate, benzotriazole silver-4
-Potassium sulfonate, silver benzotriazole-
Potassium 5-sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, silver 4-carboxybenzotriazole, silver 5-carboxybenzotriazole, silver benzotriazole-4
- Sodium carboxylate, silver benzotriazole-5-sodium carboxylate, silver benzotriazole-4-potassium carboxylate, silver benzotriazole-5-potassium carboxylate, silver benzotriazole-4-carboxylate ammonium, silver benzotriazole-5 - ammonium carboxylate,
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-methoxybenzotriazole silver, 4-hydroxy-5-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-
benzenesulfonamide benzotriazole 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)benzotriazole silver, 4-carboxy-5-methyl-
Examples include silver 7-sulfobenzotriazole. Even when used alone, these compounds
Two or more types may be used in combination. The method for preparing the organic silver salt used in the present invention will be described later, but the organic silver salt may be isolated and used by dispersing it in a binder by an appropriate means, or it may be used by dispersing it in a binder by an appropriate means. A silver salt may be prepared 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. The dye-providing substance used in the present invention is a compound capable of releasing or forming a diffusible dye upon thermal development. The term "diffusivity" as used herein means the property that the dye released or formed from the dye-providing substance can migrate from the layer containing the dye-providing substance to an adjacent layer in a stacked relationship; Regarding embodiments, for example, if the formed dye itself is a diffusible compound, the above-mentioned transfer is carried out based on this diffusivity, and in other cases, the formed dye is capable of dissolving the dye. This includes cases where the transfer is carried out by being dissolved in a solvent or by being heated and dissolved in a hot solvent. Furthermore, an embodiment in which the formed dye itself is sublimable and the formed dye sublimes and moves to an adjacent layer is also included. Here, "sublimation" is commonly used,
It includes not only the property of changing from a solid to a gas without passing through the liquid state, but also the property of melting a solid to become a liquid, and then changing from this liquid to a gas. Examples of dye-donating substances that can be used in the present invention include JP-A-57-179840 and JP-A-57-186744.
No. 58-116537, No. 58-123533, No. 57-
No. 149046, No. 59-12431, Patent Application No. 57-160698,
No. 57-205447, No. 57-224883, No. 57-224884
No. 57-229671, No. 57-229647, No. 57-
No. 225929, No. 58-33363, No. 58-33364, No. 58
Examples include the dye-donating substances described in No.-34083 and the like. The dye-providing substance preferably used in the present invention is a dye-forming substance, and those represented by the following general formula () are particularly preferable. General formula () Cp-X In the formula, Cp represents a coupler residue excluding the hydrogen atom at the active position, and Cp contains a hydrophilic group such as a sulfo group or a carboxy group, or a hydrophilic group other than the active position. It is a coupler residue that does not have a group. X represents a group that can be separated from the coupler during the coupling reaction, and further has one or more hydrophilic groups such as a sulfo group or a carboxy group, or a group containing these hydrophilic groups, and preferably has a straight chain or branched alkyl group having 8 or more carbon atoms. Examples of the coupler residue represented by Cp include those represented by the following general formulas () to ().

【formula】

【formula】

【formula】

【formula】

In the above formula, R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms). Yes, such as methyl, ethyl, butyl, t-octyl, n-dodecyl, n
Examples include groups such as -pentadecyl and cyclohexyl, but also benzyl groups and phenethyl groups may be used as alkyl groups substituted with aryl groups, such as phenyl groups), and substituted or unsubstituted aryl groups (such as phenyl groups). group, naphthyl group, tolyl group, mesityl group), acyl group (e.g. acetyl group, tetradecanoyl group, pivaloyl group, substituted or unsubstituted benzoyl group), alkyloxycarbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group) ), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group, α-
naphthoxycarbonyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), carbamoyl group (e.g. substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecyl group) carbamoyl group, N-methyl-N-dodecylcarbamoyl group,
An optionally substituted phenoxyalkylcarbamoyl group, specifically a 2,4-di-t-phenoxybutyl-carbamoyl group, a substituted or unsubstituted phenylcarbamoyl group, specifically 2-dodecyloxyphenylcarbamoyl group), substituted or unsubstituted acylamino group (e.g. n-butylamide group, laurylamide group, optionally substituted β
-Phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamidoethylamide group, β-
methoxyethylamide group), an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, an octadecyloxy group),
Sulfamoyl group (e.g. methylsulfamoyl group, n-dodecylsulfamoyl group, substituted or unsubstituted phenylsulfamoyl group, specifically dodecyl phenylsulfamoyl group), sulfonylamino group (e.g. methylsulfonyl group) represents an amino group, tolylsulfonylamino group) or a hydroxyl group. Further, R ⁶ and R ⁷ may be combined with each other to form a saturated or unsaturated 5- to 6-membered ring. ^R10 is an alkyl group (preferably 1 to 1 carbon atoms)
24 alkyl groups (e.g. methyl, butyl, heptadecyl), alkoxy groups (preferably alkoxy groups having 1 to 18 carbon atoms, e.g. methoxy, ethoxy, octadecyloxy), arylamino groups (e.g. anilino, Furthermore, halogen atoms, alkyl groups, amide groups, or anilino groups substituted with substituents such as amide groups), substituted or unsubstituted alkylamido groups (e.g. laurylamide, optionally substituted phenoxyacetamide, enoxybutanamide group), a substituted or unsubstituted arylamide group (for example, a benzamide group, and a benzamide group further substituted with a halogen atom, an alkyl group, an alkoxy group, an amide group, etc.), and the like. Furthermore, R ¹¹ , R ¹² and R ¹³ are a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms, such as a methyl group or an ethyl group). , substituted or unsubstituted alkylamide groups (e.g. laurylamide group, optionally substituted phenoxyalkylamide group, e.g. alkyl-substituted phenoxyacetamide group), substituted or unsubstituted arylamide group (e.g. benzoylamide group) ) etc. Next, R ¹⁴ is an alkyl group, preferably having 1 carbon number
~8 alkyl groups (e.g. methyl group, butyl group,
octyl group), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group), etc. Furthermore, R ¹⁵ represents an arylamino group (for example, an anilino group, an anilino group further substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imido group, etc.). Moreover, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are
It represents a group having the same meaning as the group represented by R ⁶ and R ⁷ above. Typical specific examples of the dye-providing substance represented by the general formula () include the following compounds. The dye-providing substance used in the present invention varies depending on the photothermographic composition, coating conditions, processing method, etc., but is generally 0.01 to 1.0 mole per mole of organic silver salt.
Used in a mole range, preferably 0.1 mole to 2.0 mole
It is a mole. The dye-providing substance used in the present invention is used by being contained in the heat-developable photosensitive layer or other layers. It can be dissolved and contained in a high boiling point solvent. Furthermore, in the above-described dispersion method, the dye-providing substance can be dissolved and contained in the heat-developable photosensitive layer by using a low-boiling solvent in combination with the high-boiling 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 dye-donating substance dissolved in the solvent may be an anionic surfactant such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and/or a nonionic surfactant such as sorbitan monolaurate. It can be mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing an agent, emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and added to the heat-developable photosensitive layer. The above-mentioned high boiling point solvent is used in an amount that completely dissolves the dye-providing substance, preferably in the range of 0.05 to 100 parts (parts by weight) per part (parts by weight) of the dye-providing substance. A preferable dispersion method other than the above is Fischer dispersion. Fischer dispersion refers to dissolving and dispersing a dye-providing substance having 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 added, heating and stirring (homogenizer, ultrasonic dispersion, etc.) may be performed, or the aid of a surfactant may be used. As the alkali in the alkaline aqueous solution, an inorganic base or an organic base compatible with water can be used, and after dissolving and dispersing the dye-providing substance, the pH can be adjusted as necessary. In this case, an organic or inorganic acid compatible with water can be used as the PH adjuster. The surfactant as a dispersion aid may be an anionic or nonionic surfactant, but anionic surfactants are preferred. Note that the above-mentioned Fisher dispersion is sometimes called Agfa dispersion, and the technical contents described in British Patent No. 45555, British Patent No. 465823, British Patent No. 29897, etc. can be referred to. In addition, examples of the reducing agent used in the present invention include, for example, U.S. Pat.
3764328 specification, also RD12146, RD15108,
p-phenylenediamine type and p-aminophenol type developing agents, fluoroamide phenol type and sulfonamide phenol type developing agents, hydrazone type color developing agents, etc. described in RD15127 and Japanese Patent Application Laid-Open No. 56-27132, etc. Known color developing agents such as known color developing agents or their precursors may be mentioned, but particularly preferred are those described in JP-A-56-146133 and Japanese Patent Application No. 57-225928 filed by the present applicant. p-(N,N-dialkylaminophenyl)sulfamic acid developing agent. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of organic silver salt used, the type of photosensitive silver salt, and the type of other additives, but it is usually 0.05 mol to 10 mol per mol of organic silver salt. The amount ranges from 0.1 mol to 3 mol, preferably 0.1 mol to 3 mol. In addition to the above-mentioned components, various additives may be added to the photosensitive element of the present invention as required. For example, as a development accelerator, US Pat. No. 3,220,840;
Same No. 3531285, Same No. 4012260, Same No. 4060420,
Specifications of No. 4088496 and No. 4207392 or
Alkali release agents described in RD15733, RD15734, RD15776, etc., organic acids described in Japanese Patent Publication No. 12700/1983,
−CO−, −GO ₂ −, − described in U.S. Patent No. 3667959
Examples include non-aqueous polar solvent compounds having an SO group, melt formers described in US Pat. No. 3,438,776, and polyalkylene glycols described in US Pat. No. 3,666,477 and JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 46-6077
No. 49-5019, No. 49-5020, No. 49-91215
No. 49-107727, No. 50-2524, No. 50-
No. 67132, No. 50-67641, No. 50-114217, No. 52
-33722, 52-99813, 53-1020, 53
−55115, No. 53-76020, No. 53-125014, No.
No. 54-156523, No. 54-156524, No. 54-156525
No. 54-156526, No. 55-4060, No. 55-4061
No. 55-32015, as well as West German patent no.
2140406, 2147063, 2220618, U.S. Patent No. 3080254, 3847612, U.S. Pat.
Phthalazinone, phthalicide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in the specifications of No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. , 2.3-dihydro-phthalazinedione, 2.3-dihydro-1.3-oxazine-2.4-dione, oxapyridine, 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, phthalic acid, naphthalic acid Examples include mixtures of at least one acid or acid anhydride such as phthalazine and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Furthermore, 3-amino-5-mercapto-
1.2.4-triazoles, 3-acylamino-5
-Mercapto-1.2.4-triazoles are also effective. In addition, as antifoggants, for example, Japanese Patent Publication No. 11113/1982, Japanese Patent Publication No. 90118/1973, 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 (such as N-halogenoacetamide). , N
-halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or sulfur Containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1.2.4-triazole, thiazolinthione, polysulfide compounds, etc.), and other compounds such as oxazoline, 1.2.4-triazole, phthalimide, etc. . 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-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-
Examples include 6-methyltriazine. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be carried out using a sulfur-containing compound as described in each publication of No. 50-77034. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium-based stabilizer breaker described in the specifications of No., No. 3824103, and No. 3844788, as well as U.S. Pat.
The activator stabilizer precursor described in No. 4,060,420, etc. may also be contained. In addition to the above ingredients, various additives such as spectral sensitizing dyes, antihalation dyes, fluorescent whitening agents, hardeners, antistatic agents, plasticizers, spreading agents, coating aids, etc. are added as necessary. be done. The binder used in the present invention may be either a hydrophilic or hydrophobic binder, but a hydrophilic binder is particularly preferred, and a hydrophobic binder may also be used in combination. A hydrophilic binder is one that is soluble in water or a mixture of water and an organic solvent (a solvent that is optionally miscible with water). For example, proteins such as gelatin, gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, and useful polymers include polyvinyl acetals (preferably with a degree of acetalization below 20%, e.g. polyvinyl butyral), Preferred are polyacrylamide, polyvinylpyrrolidone, ethyl cellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), etc.
It is not limited only to these. If necessary, two or more types may be used in combination. The amount of the binder is 1/10 part to 10 parts, preferably 1/4 part to 4 parts by weight per part of organic silver salt for each photosensitive layer. The layers containing the above components and other layers of the 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, and metals such as glass, paper, and aluminum. . Baryta paper, resin-coated paper, and water-resistant paper can also be used. In the heat-developable color photosensitive element of the present invention, dyes are formed or released in an imagewise manner by thermal development, and these dyes are transferred to an image-receiving element by thermal diffusion transfer to form an image. There is no need to use a specially processed image receiving element; paper, cloth, wood, glass,
Plastic, metal, etc. can be used. Particularly preferred is an image receiving element made of cellulose such as paper or cloth. Note that this does not preclude the use of the above-mentioned specially processed image-receiving sheet. Various exposure means can be used in the photosensitive elements of the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, a light source used for normal color printing, such as a tungsten lamp, mercury lamp, xenon lamp, laser beam, CRT or LED beam, 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 gradation. Furthermore, the printing from the original drawing may be done by contact printing. In addition, images projected by video cameras, etc., and image information sent from television stations can be directly transmitted to CRT or
It is also possible to send the image to OFT and form the image on a heat-developable photosensitive element using a contact lens or a lens and then print 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 provide yellow, magenta, and cyan pigments, respectively. That is, the green light-sensitive layer may contain a yellow dye-providing compound, the red light-sensitive layer may contain a magenta dye-providing compound, and the infrared light-sensitive layer may contain a cyan dye-providing compound. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
It is read by a light-receiving element such as a CCD, is stored in a memory of a computer, etc., and this information is processed as necessary through so-called image processing, and then this image information is reproduced on a CRT and used as an image-like light source. There is also a method of directly causing three types of LEDs to emit light based on the processed information. Thermal transfer from the photosensitive element of the present invention to the image receiving element is performed when the photosensitive element of the present invention is thermally developed or reheated after thermal development. For heating for thermal transfer, all methods applicable to ordinary heat-developable photosensitive materials can be used. For example, by contacting a heated block or plate, by contacting a heated roller or drum, by passing through a high temperature atmosphere, or by using high frequency heating, and furthermore, the photosensitive element of the present invention may be provided with an electrically conductive material. It is also possible to provide a layer and utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of preheating and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, increasing continuously,
Although descending or repeated heating or even discontinuous heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. Usually, the heating temperature during transfer is 80℃~200℃,
The temperature is preferably 80°C to 180°C, and the heating time is usually 1 second to 5 minutes, preferably 5 seconds to 3 minutes. For thermal transfer using the photosensitive element of the present invention, a commercially available thermal developing machine can be easily used. For example, “Image Forming Model 4634” (Sony Tektronix), “Deiberotsu Parmodule 277”
(3M Company), “Video Hard Copy Unit NWZ-
301'' (Japan Radio Co., Ltd.) etc. can be easily applied. [Examples] Examples of the present invention are shown below, but the embodiments of the present invention are not limited to these. <4-Sulfobenzo Preparation of triazole silver salt> 20 g of 3-sulfobenzotriazole and 4 g
of sodium hydroxide in ethanol-water (1:1)
It was added to 300 ml of the mixed solution and dissolved. 20 ml of 5N silver nitrate solution was added dropwise to this solution. At this time, 5N sodium hydroxide solution was also added dropwise at the same time to bring the pH to 7-8.
maintained. This solution was stirred for 1 hour at room temperature and then made up to 400 ml with water to prepare a 4-sulfobenzotriazole silver solution. Example 1 1520 mg of the exemplary dye-providing substance was dissolved in a mixture of 520 mg of dioctyl phthalate and 1.6 ml of ethyl acetate. This solution was mixed with 6 ml of a 5.5% gelatin aqueous solution containing a surfactant, and water was added to make 12 ml.
Dispersion was performed using a homogenizer to obtain a dispersion of the dye-providing substance. The above 4-sulfobenzotriazole silver solution 4
ml, 6.5 ml of dye-donor dispersion, and further add 730 mg of polyvinylpyrrolidone (molecular weight 30,000),
After adding 520 mg of pentaerythritol, 310 mg of polyethylene glycol (molecular weight 400), 3 ml of water, and 200 mg of the following developer, the pH was adjusted to 5.5 with 3% citric acid. Silver iodobromide with an average particle size of 0.05 μm was added to this dispersion in an amount of 3×10 ⁻⁴ mol in terms of silver, and the mixture was coated onto a polyethylene terephthalate base using a wire bar to a wet film thickness of 65 μm. , a photosensitive layer was applied. developer Next, 3 g of carnauba wax was dissolved in 30 ml of ethyl acetate, and the solution was coated on the photosensitive layer using a wire bar to a wet film thickness of 70 μm to form a heat-fusible layer. After drying the resulting photosensitive element, a white exposure of 32,000 CMS (candela meter seconds) was applied through a step wedge. Next, baryta paper, white paper for a dry copying machine (U-Bix, manufactured by Konishiroku Photo Industry Co., Ltd.), or image receiving paper coated with vinyl chloride on baryta paper was placed on the coated surface of the exposed sample, and the surface temperature was 140°C. The paper was pressed and heated for 60 seconds using a metal heat block, and then the image-receiving paper was peeled off, and the density of the dye image transferred to each image-receiving paper was measured. Furthermore, an image was obtained by the same operation using an image receiving paper in which vinyl chloride was coated on baryta paper. The results are shown in Table-1. Example 2 On the photosensitive layer of Example 1, 3 g of dimethylurea and 3 g of polyvinyl butyral were dissolved in 30 ml of methanol and coated with a wire bar to a wet film thickness of 70 μm to obtain a heat-fusible layer. After drying the obtained photosensitive element, it was exposed to light in the same manner as in Example 1, and thermally developed using the same image receiving paper as in Example 1 to obtain a transferred image. The results are shown in Table-1. Example 3 The same sample as in Example 1 was prepared, except that 850 mg of Dye-Providing Substance 4 was used instead of Dye-Providing Substance 1 in Example 1, and the same exposure and heat development as in Example 1 were performed. The results are shown in Table-1. Comparative Examples 1 and 2 Samples of the photosensitive elements of Examples 1 and 3 except for the heat-fusible layer were subjected to the same exposure and heat development as in Example 1, respectively. The results are shown in Table-1. Example 4 6 ml of the dye dispersion of Example 1 and 4 ml of the sulfobenzotriazole silver solution were mixed, and then 450 mg of polyvinylpyrrolidone (molecular weight 30,000), 375 mg of pentaerythritol, 225 mg of polyethylene glycol (molecular weight 400), 3 ml of water, and 200 mg of the above developer were added. was added, and the pH was adjusted to 5.5 with 3% citric acid. Silver iodobromide having an average particle size of 0.125 μm and red sensitivity was added to this dispersion in an amount of 3×10 ⁻⁴ mol in terms of silver, and a wet film thickness was formed on the polyethylene terephthalate base.
The first photosensitive layer was coated with a wire bar to a thickness of 65 μm. Then add 4 ml of sulfobenzotriazole silver solution and
Mix 3 ml of 2.5% gelatin solution and add 450 mg of polyvinylpyrrolidone and pentaerythritol.
Added 375mg, polyethylene glycol 225mg,
Water was added to make 13 ml. This solution was applied onto the first photosensitive layer to form an intermediate layer. Next, a second photosensitive layer having the same composition as the first photosensitive layer was used, except that the dye-providing substance in the first photosensitive layer was replaced with Dye-donating Substance 4, and the silver halide was replaced with silver iodobromide having an average grain size of 0.125 μm and having green sensitivity. Two photosensitive layers were applied. Furthermore, a heat-fusible layer having the same components as in Example 1 was applied to obtain a multilayered photosensitive element. This sample was passed through a step wedge, exposed to white, red and green at 1600 CMS, baryta paper,
After overlapping baryta paper and image-receiving paper coated with vinyl chloride and developing at 140° C. for 1 minute, the image-receiving paper was peeled off to obtain a transferred image on each image-receiving paper. Table 2 shows the density of the obtained image.

【table】

[Table] As shown in the above examples, by providing a heat-fusible layer on the outer layer of the photographic constituent layer, the transferability of dyes to plain paper is improved, and the transfer density is sufficient to use plain paper as image-receiving paper. An image is obtained. Furthermore, since the adhesion to the image-receiving paper and the releasability after development are improved, there is also the effect of increasing the transfer density and reducing transfer unevenness on the surface-treated image-receiving paper.

Claims (1)

[Claims] 1. A heat-developable color photosensitive material having, on a support, a photographic constituent layer containing at least a photosensitive silver halide, an organic silver salt, a reducing agent, a dye-providing substance capable of releasing or forming a diffusible dye by heat development, and a binder. 1. A heat-developable color photosensitive material, characterized in that the outer layer of the photographic constituent layer is a heat-fusible layer containing a heat-fusible substance.