JPH0346812B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel heat-developable color photosensitive material,
Specifically, it relates to a heat-developable color photosensitive material that obtains an image by thermally transferring an imagewise distribution of a diffusible dye formed in a heat-developable photosensitive element to an image-receiving layer, and more specifically, it relates to a heat-developable color photosensitive material that obtains an image by thermally transferring an imagewise distribution of a diffusible dye formed in a heat-developable photosensitive element to an image-receiving layer. The present invention relates to a heat-developable color photosensitive material in which the substance is non-diffusible and the dye-providing substance forms a magenta dye with good diffusibility, so that the separation of the dye-providing substance and the diffusible dye is enhanced during thermal transfer. [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 processing chemicals may pose a threat to the human body, or There are many problems, such as concerns about contamination of workers by treatment 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 in that the development process is carried out by heat treatment have been known for a long time, and are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924. A photosensitive material comprising a developer 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. 15108, No. 15127, No.
U.S. Patent No. 3180731, RD No. 13443, U.S. Patent No. 14347, etc. contain leuco dyes. U.S. Patent No. 4235957, RD No. 14433,
No. 14448, No. 15227, No. 15776, No. 18137, and No. 19419, etc., include U.S. Patent No. 4124398, U.S. Pat.
No. 4,124,387 and No. 4,123,273 describe 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. 57-122596 filed by the present applicant describes a method in which a sublimable dye is released by heat development and transferred to an image-receiving layer. However, with these proposals regarding color heat-developable photosensitive materials, it is difficult or impossible to bleach or fix the simultaneously formed black, white, and silver images, or even if it is possible, wet processing is required. That is. Furthermore, it is also possible to obtain a color image on the image-receiving layer by thermally diffusing and transferring the dye without requiring wet processing, but in this case, the dye-donating substance is also transferred to the image-receiving layer at the same time as the dye is diffused. There is a problem of contamination of the layer. This means that when the dye-donating substance is a dye-releasing substance that produces diffusible dyes or sublimable dyes, contamination is particularly severe because the dye-donating substance itself is a colored compound, and when the dye is released, In addition to the formed color image, unnecessary dyes are also transferred, which poses major problems such as contamination. On the other hand, when the dye-providing substance is a colorless or white dye-forming substance such as a so-called ordinary photographic coupler, this also poses a problem because it causes yellowing and staining of the image-receiving layer during image storage. This has the disadvantage that when the dye-donating substance is a dye-releasing substance, compared to the case where it is a dye-forming substance, the compound itself is colored, and the image-receiving layer is heavily contaminated. It means that. Another problem is that when the dye-donating substance is a dye-releasing substance, compared to when it is a dye-forming substance, because the compound is colored, it becomes extremely desensitized. It also has From the above viewpoints, dye-forming substances are more preferable than dye-releasing substances as dye-providing substances used in heat-developable photosensitive materials. Furthermore, when the dye-providing substance is a dye-forming substance, for example, in the case of a photosensitive material in which light-sensitive layers each spectrally sensitized to different wavelength ranges are layered, color turbidity may occur as long as the dye-providing substance can diffuse between the layers. Otherwise, there is a problem that it causes poor color development.
Therefore, from the above point of view, it is absolutely unacceptable for the dye-providing substance to diffuse into the image-receiving layer or other layers during thermal development. Therefore, the dye-providing substance used in the heat-developable color light-sensitive material must be a sufficiently non-diffusible compound. When the dye-donating substance is a dye-forming substance, the removed and unnecessary active site substituents may be transferred to the image-receiving layer, resulting in staining of the image-receiving layer, or contamination during image storage. Needless to say, non-diffusion is preferable since it can also be a cause. Under the above background, as a result of extensive research into preferable dye-donating substances, the present inventor previously disclosed in Japanese Patent Application No. 58-33364 that the dye-donating substance has a water-soluble group and that the dye-donating substance has a heat-soluble group. We proposed a compound that can form a dye without a diffusible water-soluble group upon development. As a result of further research, the inventor of the present invention found that among the compounds proposed above, especially those that give magenta dye, there is a drawback that fogging density increases when the image density is increased, and the present inventors have found that the above-mentioned previously proposed compounds have the disadvantage that fogging density increases when the image density is increased. As a result of extensive research, we have completed the present invention. [Object of the Invention] An object of the present invention is to provide a heat-developable color photosensitive material in which the separability of the dye-forming substance residue and the diffusible dye formed during thermal transfer is improved. Another object of the present invention is to provide a dye-providing substance that can provide a transferred image with high density and a magenta transferred image with little fog. [Structure of the Invention] In order to achieve the above object, the present inventors have conducted intensive research and found that a dye donor capable of forming a dye on a support by at least a photosensitive silver halide, an organic silver salt, a reducing agent, and heat development. In a heat-developable color light-sensitive material having at least one photographic constituent layer containing a substance and a hydrophilic binder, the dye-providing substance is a magenta dye-providing substance represented by the following general formula [] or []. , have discovered that the above object can be achieved, and have completed the present invention. In the formula, R ₁ is an alkyl group, preferably an alkyl group having 6 or less carbon atoms, an aryl group, preferably a phenyl group, an alkylamino group, preferably an alkylamino group having 6 or less carbon atoms, an arylamino group, preferably a phenyl group, or an aryl group. Group preferably has 7 carbon atoms
R represents an acyl group, a ureido group (which may be substituted with an alkyl group or an aryl group), or a cyano group, and R ₂ is a halogen atom, a hydrogen atom, an alkyl group, preferably an alkyl group having up to 3 carbon atoms, or an alkoxy group, preferably an alkoxy group having 6 or less carbon atoms, Y represents a hydrophilic group, and X
represents a group substituted with one or more hydrophilic groups, preferably a group substituted with one or more sulfo groups or carboxy groups and having an alkyl chain having 8 or more carbon atoms, and J is preferably a divalent bonding group. is −CO−, −
SO ₂ -, -NH-, -S-, -O-,

[Formula] − NHSO ₂ −,

【formula】

【formula】

[Formula] etc., l represents an integer from 1 to 3, m represents 0 or 1, n represents 1 or 2, p and q represent 0, 1 or 2 (however, p and q are both are not 0), r is 1 (when n=2)
or 2 (when n=1). Examples of the hydrophilic group represented by Y and the hydrophilic group substituted with the group represented by Thio group, carboxy group, thiocarboxy group, carboxyimide acid group, hydrazonic acid group, carbohydrazonic acid group, hydroxamic acid group, carboxymic acid group, hydroxamic acid group, carbohydroxamic acid group, sulfinimidic acid group, sulfonimide Acid groups, sulfinohydrazonic acid groups, sulfonohydrazonic acid groups, sulfinohydrazonic acid groups, sulfonohydrazonic acid groups, and those that can form salts with these groups (e.g., alkali metal salts, ammonium salts, etc.), with sulfo groups and carboxy groups being particularly preferred. The present invention will be explained in detail below. The magenta dye-providing substance represented by the general formula [] or [] is a compound having a hydrophilic group, and is a compound capable of forming a dye having no diffusible hydrophilic group upon thermal development. The "diffusibility" of the diffusible dye formed during the above heat development refers to the fact that the magenta dye formed from the dye-providing substance moves from the layer containing the dye-providing substance to an adjacent layer in a stacked relationship. Regarding the mode of this movement, for example, if the produced dye itself is a diffusive compound, the above-mentioned movement is performed based on this diffusivity; This includes cases where the transfer is carried out by dissolving the dye in a dye solvent or by heating and dissolving it 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, the term "sublimation" refers not only to the commonly used property of changing from a solid to a gas without passing through the liquid state, but also to the property of melting a solid to become a liquid, and then changing from this liquid to a gas. It also includes properties. The magenta dye-donor substance represented by the general formula [] or [] used in the present invention is the 3-position (hereinafter referred to as
A magenta dye is formed by reacting with the oxidized product of the color developing agent at the active site (referred to as the active site), but in this case, if the magenta coupler core has a small molecular weight (preferably a molecular weight of 400 or less) and does not contain a hydrophilic group. has the property of being highly diffusible in hydrophilic binders. In addition, the presence of a group containing a hydrophilic group such as a sulfo group or a carboxy group in the substituent at the active site makes the dye-donating substance immobilized during development, and the substituent at the active site is released during dye formation. Therefore, it is not inconvenient for the forming pigment. Details will be described later. Among the magenta dye-providing substances represented by the above general formula [] or [], particularly preferred are the dye-donating substances shown by the following general formula []. General formula [] In the formula, R ₁ , R ₂ , X, Y, 1, p and q have the same meanings as defined in the general formula []. Typical specific examples of the magenta dye-providing substance represented by the general formula [] or [] used in the present invention will be described below, but the invention is not limited thereto. The magenta dye-providing substances of the present invention may be used alone or in combination of two or more. The dye-providing substance used in the present invention is generally obtained by reacting a 3-pyrazolone magenta coupler with an aliphatic or aromatic dialdehyde having a hydrophilic group, or by reacting a 3-pyrazolone magenta coupler with an aliphatic or aromatic dialdehyde. It can be obtained by introducing a substituent having a water-soluble group into a compound obtained by reacting with an aromatic dialdehyde. Next, a specific synthesis example will be shown. Synthesis Example 1 Synthesis of dye-donating substance (3) 8.65g of 1-phenyl-3teacetylamino-
5-pyrazolone and 1.8 g of 5-nitro-isophthalaldehyde were added to 100 ml of ethanol, heated under reflux for 2 hours, and then the ethanol was removed. The obtained solid was added to 100 ml of acetone, 5 g of tin powder and 5 ml of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature for 1 hour. After heating under reflux for another 2 hours, sodium carbonate was added under cooling to bring the pH to about 6.0. . This reaction solution was filtered and concentrated, and the precipitated crystals were filtered to obtain an amine intermediate. 2.8 g of 2-sulfostearic acid was added to a mixed solution of acetonitrile (12 ml) and pyridine (6 ml), 1 ml of benzenesulfonyl chloride was added, and after refluxing for 1 hour, the mixture was cooled to 30°C and the above amine intermediate (7.3 g) Acetonitrile (20ml)
The solution was added dropwise. After dropping, reflux for 3 hours, filter, concentrate the filtrate, add 200 ml of methanol, filter again, concentrate the filtrate, add saturated brine (200 ml),
The precipitate was collected by filtration, added to 200 ml of methanol and filtered again, and the filtrate was concentrated to obtain the target product containing impurities. This was purified by column chromatography using chloroform-methanol (9:1) as a developing solvent to obtain 4.2 g of the desired product. Synthesis Example 2 Synthesis of dye-donating substance (14) 18.5g of 2-(N-dodecanyl-N-methyl)
Amino-5-sulfoaniline was dispersed in a mixed solution of 200 ml of toluene and 40 ml of pyridine, a solution of 3.5 ml of phosphorus trichloride in toluene (100 ml) was added dropwise, and the mixture was reacted at 120° C. for 1.5 hours. Cool this reaction solution and
g of terephthalaldehydic acid in toluene (50ml)
The solution was added dropwise, and the mixture was reacted at 120° C. for 2 hours after the addition.
The reaction solution was filtered, and the precipitate was added to 200 ml of methanol and dissolved by heating. After removing insoluble materials by filtration, the methanol solution was concentrated. Next, 200ml of ethanol was added and dissolved, and 21.6g of 1-phenyl-3
After adding -acetylamino-5-pyrazolone and refluxing for 2 hours, the mixture was concentrated and purified in the same manner as in Synthesis Example 1 to obtain 24.5 g of the desired product. The dye-donating substance used in the present invention produced by the above synthesis method has a hydrophilic group or a hydrophilic group as a group capable of leaving at the active site of a coupler molecule having a hydrophobic group as represented by the above general formula []. It is a compound in which a group having a group is substituted. Therefore, in the hydrophilic binder containing this compound,
Due to its affinity, it becomes non-diffusible, but during thermal development, the hydrophilic group at the active site is removed by an oxidative coupling reaction, and the dye that has lost its hydrophilic group is no longer a hydrophilic binder (described later). The dye loses its affinity with the dye, becomes completely hydrophobic, and diffuses into the image-receiving layer, where it has a stronger affinity, forming a dye image on the image-receiving layer. On the other hand, the hydrophilic components separated from the active sites during thermal development still have an affinity for the hydrophilic binder, so they remain in the hydrophilic binder and do not diffuse into the image-receiving layer. This effect is particularly great when the image-receiving layer is made of a hydrophobic substance. Therefore, according to the present invention, the separability between the dye-providing substance residue and the diffusible dye during thermal development is significantly improved, the occurrence of staining of the image-receiving layer is completely prevented, and staining does not occur during storage. The numbers have also decreased significantly. Also, in the case of a multilayer structure, a dye image without color turbidity can be obtained. Furthermore, in the dye-donating substance used in the present invention, it is very important to introduce a ballast group into the active site of the coupler residue in order to improve the non-diffusibility of the compound, and to make this ballast group have the above-mentioned hydrophilic group. This is preferable. That is, by providing the dye-providing substance with a ballast group, the non-diffusivity of the dye-providing substance in the hydrophilic binder before thermal development can be further improved. In addition, during thermal development, the ballast group component having a hydrophilic group detached from the active site of the coupler molecule can further strengthen immobilization in the hydrophilic binder in combination with the hydrophilic group. This makes it possible to further enhance the above-mentioned effects. Furthermore, the dye-donating substance used in the present invention is
Since it is colorless or nearly white, it does not color the layer and does not impair effective sensitivity. The dye-providing substance used in the present invention varies depending on the photothermographic composition, coating conditions, processing method, etc., but is generally used in the range of 0.01 mol to 10 mol, preferably 0.1 mol, per 1 mol of organic silver salt. ~2.0 mol. The dye-providing substance used in the present invention is used by being contained in the heat-developable photosensitive layer or other photographic constituent layers. For example, in order to contain it in the heat-developable photosensitive layer,
They can be incorporated in a high boiling solvent as described in US Pat. No. 2,322,027, which relates to a method for dispersing couplers. 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 alkylbenzenesulfonic acid and alkylnaphthalenesulfonic 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, 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, and preferably in a range of 0.05 to 100 parts per part 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. The dye-providing substance used in the present invention is obtained by using a hydrophilic binder described below in the heat-developable photosensitive layer, and dispersing the fissure or oil protection in the hydrophilic binder as described above. Since there is no need to grind using a ball mill or sand mill, the dye can be finely and stably dispersed in the heat-developable photosensitive layer in a short time, and the transfer density of the dye image can be improved. Ta. In addition, in the present invention, a hydrophilic binder is used as the binder for the heat-developable photosensitive layer as described later, so when the heat-developable photosensitive layer is coated on a support, it is possible to apply the coat using a non-organic solvent, that is, an aqueous system. In particular, when gelatin is used as a binder, its setting property can be utilized, so it is non-polluting, and horizontal coating is not necessarily required, which simplifies the process for manufacturing photosensitive materials. The heat-developable photosensitive layer of the present invention contains photosensitive silver halide similarly to the dye-providing substance described above. 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 photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 1.5 μm to about 0.001 μm, more preferably about 0.5 μm to about 0.001 μm. It is approximately 0.01 μm. 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. 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, an _NH4 group, or a metal atom, and X represents Cl, Br). Or I, n is M is H atom,
When it is an NH ₄ group, it shows I, 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 2.0 mol, preferably 0.01 mol to 0.5 mol, per 1 mol of organic silver salt. It is. 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 obtained by adding various spectral sensitizing dyes to the silver halide emulsion. I can do it. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holobolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the 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-mentioned 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. 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, 52-
No. 31728, No. 52-13731, No. 52-141222, No. 53
-36224, 53-37610, U.S. Patent No.
Silver salts of aliphatic carboxylic acids described in specifications such as No. 3330633 and No. 4168980, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc. Also, aromatic silver carboxylates such as silver benzoate, silver phthalate, etc., silver salts having an imino group, such as silver benzotriazole, silver saccharin, silver phthalazinone, silver phthalimide, etc., and silver compounds having a mercapto group or a thione group. salts such as silver 2-mercaptobenzo-oxazole, silver mercaptooxadiazole, silver mercaptobenzothiazole, 2
-mercaptobenzimidazole silver, 3-mercapto-phenyl-1,2,4-triazole silver,
In addition, 4-hydroxy-6-methyl-
Examples include 1,3,3a,7-tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver, and the like. 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 those 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-benzotriazole-5-ylazo-4-methoxy-1-naphthol silver salt, 1-benzotriazol-5-ylazo-2-naphthol silver salt, Examples include N-benzotriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt. 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 ₃ represents a nitro group, R ₄ and R ₅ 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 ₆ is 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. R ₇ 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 (e.g. methyl group, ethyl group, propyl group), each of which may have a substituent, aryl group ( 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 ₆ include methyl, ethyl, acetyl, etc., and examples of substituents for sulfamoyl include methyl, ethyl, acetyl, etc. be able to. Furthermore, the above
Substituents for the alkyl group in R ⁷ include, for example, carboxy group, ethoxycarbonyl group, etc. Substituents for the aryl group include, for example, sulfo group, nitro group, etc. Substituents for the alkoxy group include, for example, carboxy group, ethoxycarbonyl 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-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 the organic silver salt used is 0.05g per 1m of support.
-10.0g, preferably 0.2g - 20g. Further, examples of the reducing agent used in the heat-developable color photosensitive material of the present invention include, for example, US Pat. No. 3,531,286;
No. 3761270 and No. 3764328, as well as RD12146, RD15108, RD15127 and JP-A-Sho.
p-phenylenediamine-based and p-aminophenol-based developing agents described in Publication No. 56-27132, etc.;
Known color developing agents such as fluoroamide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents, or their precursors are particularly preferred, but particularly preferred are those disclosed in JP-A-56-146133 and the present applicant. This is a p-(N,N-dialkylaminophenyl)sulfamic acid developing agent described in Japanese Patent Application No. 1983-225928. 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 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. 3220840, 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
-, -SO ₂ -, non-aqueous polar solvent compound having -SO- groups, melt former described in US Pat. No. 3,438,776, US 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. 56-4060
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, phthalide, 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 combinations of one or more of these with imidazole compounds a mixture or a mixture of at least one acid or acid anhydride such as phthalic acid or naphthalic acid and a phthalazine compound;
Furthermore, phthalazine, maleic acid, itaconic acid,
Examples include combinations of quinolinic acid, gentisic acid, and the like. In addition, the applicant filed a patent application in 1983.
3 described in No. 73215 and Specification No. 57-76838
-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, West German Patent No. 2617907, etc., 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, diterpene acid, thiosulfonic acid, etc.), or sulfur Containing compounds (e.g. mercapto compound-releasing compound, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthione, polysulfide compound, etc.), others, oxazoline, 1,2,4
-Compounds such as triazole and phthalimide are mentioned. 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.
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 precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain activator stabilizer precursors and the like as described in No. 4,060,420 and the like. In addition to the above-mentioned components, the heat-developable color photosensitive material of the present invention may further contain spectral sensitizing agents, antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, spreading agents, etc. Various additives, coating aids, etc. are added. Although a hydrophilic binder is used as the binder in the heat-developable color photosensitive material of the present invention, a hydrophobic binder may also be used in part. The hydrophilic binder used in the present invention refers to one that is soluble in water or a mixed solution of water and an organic solvent (a solvent that is optionally miscible with water). For example, proteins such as gelatin, gelatin derivatives, cellulose derivatives,
Natural substances such as polysaccharite such as dextran, gum arabic, etc. and effective polymers include polyvinyl acetal (preferably with a degree of acetalization of less than 20%, e.g. polyvinyl butyral), polyacrylamide, polyvinylpyrrolidone, ethylcellulose, polyvinyl alcohol (preferably those with a conversion rate of 75% or more), but are not limited to these. If necessary, two or more types may be used in combination. The amount of binder is 1 organic silver salt per each photosensitive layer.
1/10 to 10, preferably 1/10 to 10 parts by weight
4 to 4 parts. 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. The light-sensitive material of the present invention basically includes (1) photosensitive silver halide, (2) organic silver salt, (3) hydrophilic binder, (4) dye-donating substance of the present invention, and (5) the same layer. Contains reducing agent. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, one photosensitive layer may be divided into two layers, and the dye-providing substance of the present invention may be added to the above-mentioned (1),
(2), (3), and (5) are divided into two or more photographic constituent layers if they are in a state where they can react with each other, such as when they are contained in one photosensitive layer adjacent to another photosensitive layer containing the components. It may also be included. The heat-developable color photosensitive material of the present invention may have two or more photosensitive layers having different color sensitivities, and may have various photographic structures such as an overcoat layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer. It may have layers. A dye image can be formed in the heat-developable color light-sensitive material by imagewise exposure and heat treatment. Thermal transfer can be performed using a hot solvent that melts with heat. It is also possible to use a thermal transfer method as described in British Patent No. 1590957. The photosensitive material of the present invention (hereinafter referred to as the photosensitive element of the present invention) is imagewise exposed and then thermally developed to form an imagewise distribution of a heat transferable dye from the dye-providing substance, and the image When applied to a color thermal diffusion transfer method in which at least a portion of the image distribution is thermally transferred to an image-receiving layer in stacked relationship with the photosensitive element of the present invention, the high-density image formed on the image-receiving layer is improved. give an image. The image-receiving layer only needs to have the function of receiving the dye released or formed by thermal development, and may be a mordant used in dye diffusion transfer type photosensitive materials or JP-A-57-
It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower as described in Japanese Patent No. 207250 or the like. Specific examples of the mordant include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, US Pat. No. 2,548,564,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
2,675,316, aminoguanidine derivatives as disclosed in U.S. Pat. No. 2,882,156, U.S. Pat.
No. 3625694, No. 3859096, British Patent No. 1277453,
A mordant capable of crosslinking with gelatin etc. disclosed in US Patent No. 2011012, US Patent No. 3958995,
Aqueous sol type mordant disclosed in No. 2721852 and No. 2798063, water-insoluble mordant disclosed in JP-A-50-61228, U.S. Patent No. 3788855, OLS No. 2843320, JP Showa 53-
No. 30328, No. 52-155528, No. 53-125, No. 53-
No. 1024, No. 54-74430, No. 54-124726, No. 55
−22766, U.S. Patent No. 3642482, U.S. Patent No. 3488706,
No. 3557066, No. 3271147, No. 3271148, Special Publication No. 55-29418, No. 56-36414, No. 57-12139,
Examples include various mordants disclosed in RD12045 (1974). Particularly useful mordants are polymers containing ammonium salts, as described in US Pat. No. 3,709,690.
For example, as a polymer containing ammonium salt,
In polystyrene-co-N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, the ratio of styrene to vinylbenzylammonium chloride is from 1:4 to 4:1, preferably 1:1. A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. A transfer solvent can be used to transfer the dye from the heat-developable photosensitive layer to the image-receiving layer. The transfer solvent includes a low boiling point solvent such as methanol, ethyl acetate, diisobutyl ketone, tri-n-cresyl phosphate,
A high boiling point solvent such as tri-n-nonyl phosphate or di-n-butyl phthalate is used. In the case of a high boiling point solvent, it can be emulsified in gelatin using a suitable emulsifier and added to the image-receiving layer. Examples of the heat-resistant organic polymer substances include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, and polyvinyl. Alcohol, polyacetals such as polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylallylamide, p-cyanophenyl group, pentachlorophenyl group, and Polyacrylate with 2,4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene Glycol dimethacrylate, poly-2-
Examples include polyesters such as cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also, Polymer Handbook 2nd CD.
Brandrup, EHImmergut ed.) John Wiley &
Glass transition temperature listed in Sons Publishing,
Synthetic polymers below 40°C are also useful. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetate, such as triacetate and diacetate;
Polyamides made from combinations such as terephthalic acid with heptamethylene diamine, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxib Examples include polyester made from a combination of tan and ethylene glycol, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, etc. as a modifier is also effective. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer solely from a member (for example, a film) made of the above-mentioned polymer (combined image-receiving layer/support type). Further, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer provides a reflective color image when the transferred color image is viewed from the transparent support side of the image-receiving layer. [Examples] Examples of the present invention are shown above, but the embodiments of the present invention are not limited to these. <Preparation of 4-sulfobenzotriazole 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, a 5N sodium hydroxide solution was also added dropwise at the same time to maintain the pH at 7-8. After stirring this solution for 1 hour at room temperature,
A 4-sulfobenzotriazole silver solution was prepared by making up the volume to 400 ml with water. Example 1 4.1 g of exemplary dye-providing substance (1) and 1.6 g of a 1% aqueous solution of di(2-ethylhexyl)-2-sulfosuccinic acid
ml, 2.8 ml of water, and 2 ml of methanol, and after adding 4 ml of 1N sodium hydroxide solution,
17.5 ml of 8% aqueous gelatin solution was added. This dispersion was neutralized with 8% citric acid and then made up to 30 ml with water. The above 4-sulfobenzotriazole silver solution 4
ml and 6 ml of a dispersion of a dye-donating substance, and further add 730 mg of polyvinylpyrrolidone (molecular weight 30,000), 520 mg of pentaerythritol, 310 mg of polyethylene glycol (molecular weight 400), 3 ml of water, and the following developer.
After adding 200 mg, the pH was adjusted to 5.5 with 8% 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 support using a wire bar so that the wet film thickness was 65 μm. . The sample obtained by drying the above coating was passed through a step wedge and exposed to light at 30,000 CMS (candela meters seconds). Next, an image receiving paper coated with vinyl chloride on baryta paper was placed on the coated surface of the exposed sample, and the image was pressed and heated for 60 seconds using a metal heat block with a surface temperature of 160°C.Then, the image receiving paper was peeled off and transferred to the image receiving paper. The dye image density (transmission density) was measured. The results are shown in Table 1 below. Example 2 A sample prepared using the same method as in Example 1 except that polyvinylpyrrolidone was replaced with polyvinyl alcohol (degree of polymerization 400) was prepared, and exposed and exposed in the same manner as in Example 1.
I developed it. The results are also shown in Table 1. Example 3 A sample was prepared using the same process as in Example 1, except that the polyethylene glycol heat solvent was replaced with dimethylurea (310 mg), and the same exposure and development as in Example 1 was performed. The results are also shown in Table 1. Example 4 Example 1 except that Exemplary Dye-Providing Substance (3) was used instead of Exemplary Dye-Providing Substance (1) as the dye-providing substance.
A sample prepared using the same method as in Example 1 was prepared, and exposed and developed in the same manner as in Example 1. The results are also shown in Table 1. Example 5 A sample was prepared using the same method as in Example 1 except that Exemplified Dye Donor Substance (13) was used instead of Exemplified Dye Donor Substance (1) as the dye donor substance.
The same exposure and development were performed. The results are also shown in Table 1. Example 6 The sample of Example 1 was exposed to the same light as in Example 1, and then an image-receiving layer made of polyethylene terephthalate was placed on top of the sample and heated under pressure for 60 seconds using a metal heat block with a surface temperature of 160°C. The film was peeled off and the transferred density was measured by transmission density. The results are also shown in Table 1. Comparative Examples 1 and 2 The following dye-donating substances (A) and
Two types of samples were prepared using the same process as in Example 1 except that (B) was used, and the same exposure and development as in Example 1 were performed. The results are also shown in Table 1.

【table】

[Table] As is clear from the results in Table 1 above, the photosensitive element using the magenta dye-providing substance of the present invention is
It can be seen that it exhibits excellent effects such as a large maximum density (Dmax) and a small fog (Dmin).

Claims (1)

[Scope of Claims] 1. A photographic structure comprising at least one layer on a support, containing at least a photosensitive silver halide, an organic silver salt, a reducing agent, a dye-providing substance capable of forming a dye by heat development, and a hydrophilic binder. A heat-developable color photosensitive material having a layer, wherein the dye-providing substance is a magenta dye-providing substance represented by the following general formula [] or []. [In the formula, R ₁ is an alkyl group, an aryl group, an alkylamino group, an arylamino group, an acylamino group,
represents a ureido group or a cyano group, _R2 represents a halogen atom, a hydrogen atom, an alkyl group or an alkoxy group, Y represents a hydrophilic group, X represents a group substituted with one or more hydrophilic groups, J represents a divalent bonding group, l represents an integer of 1 to 3, m
represents 0 or 1, n represents 1 or 2, p
and q represent 0, 1 or 2 (however, p and q are both not 0), r is 1 (when n=2) or 2
(when n=1). ]