JPH029336B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable photosensitive material that forms a color image by transferring a diffusible dye formed by heat development, and particularly relates to a heat-developable photosensitive material that uses a novel development accelerator-releasing compound to form a color image. The present invention relates to a heat-developable photosensitive material capable of producing images with high sensitivity, high density, and low fog. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may affect the human body, or the processing room and work area may be affected. There are many problems, such as concerns about contamination of people by the above-mentioned chemicals, and further consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be carried out by heat treatment are attracting attention as photosensitive materials that meet the above-mentioned requirements. Such heat-developable photosensitive materials are described in, for example, Japanese Patent Publication Nos. 43-4921 and 43-4924, which disclose photosensitive materials comprising an organic silver salt, silver halide, and a reducing agent. Attempts have been made to improve such heat-developable photosensitive materials and obtain color images by various methods. For example, U.S. Pat. No. 3,531,286, U.S. Pat. No. 3,761,270, and U.S. Pat. No. 3,764,328 disclose thermal development in which a color image is formed by the reaction of an oxidized product of an aromatic primary amine developing agent with a coupler. A color photosensitive material is disclosed. Further, Research Disclosure No. 15108 and No. 15127 disclose a heat-developable color photosensitive material in which a color image is formed by the reaction of an oxidized product of a sulfonamide phenol or sulfonamide aniline derivative developing agent with a coupler. has been done. However, in these methods, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in the problem that the color image becomes cloudy. To solve this problem, there is a method of removing the silver image by liquid processing or transferring only the dye to another layer, such as an image receiving sheet having an image receiving layer, but it is necessary to distinguish between unreacted materials and the dye. The problem is that it is not easy to transfer only the dye. In addition, using an organic imino silver salt having a dye part in Research Disclosure No. 16966, the imino group is liberated in the exposed area by heat development, and a color image is transferred onto the image-receiving layer as a transfer paper using a solvent. A heat-developable color photosensitive material is disclosed. However, this method has the problem that it is difficult to suppress the release of dye in areas not exposed to light, and it is not possible to obtain clear color images. Also, JP-A-52-105821, JP-A No. 52-105822,
Publications No. 56-50328, U.S. Patent No. 4235957, Research Disclosure No. 14448,
No. 15227 and No. 18137, etc., disclose heat-developable color photosensitive materials in which a positive color image is formed by a heat-sensitive silver dye bleaching method. However, this method requires extra steps and photographic construction materials, such as stacking and heating sheets containing activators to speed up the bleaching of the dyes, and the resulting color images do not survive long-term storage. Another problem is that it is gradually reduced and bleached by coexisting free silver and the like. Further, in the specifications of U.S. Patent No. 3180732, U.S. Patent No. 3985565, and U.S. Patent No. 4022617, as well as Research Disclosure No. 12533, heat-developable color photosensitive materials are disclosed that utilize leuco dyes to form color images. ing. However, this method has the problem that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. As a method to compensate for the drawbacks of the above-mentioned method, heat-developable color photosensitive materials are known in which a diffusive dye is formed in an imagewise manner and transferred to form a dye image on the image receiving area. No. 179840,
No. 57-186744, No. 58-58543, No. 59-79247
No. 58-149046, No. 58-149047, No. 59-
No. 12431, No. 59-48765, No. 59-116741, No. 59
−124327, No. 59-124329, No. 59-166954,
It is described in publications such as No. 59-159158 and No. 59-181345. However, these methods also have the disadvantage that a color image with sufficient density cannot be obtained due to low developability, or that fog increases if high temperature development or long-term development is performed to improve developability. are doing. In addition, certain compounds are effective in increasing developability and obtaining high-density images;
At the same time, it also has the disadvantage of increasing fog. [Object of the Invention] An object of the present invention is to solve the problems of the prior invention. That is, an object of the present invention is to provide a novel development accelerator that can be used in heat-developable photosensitive materials. Another object of the present invention is to provide a heat-developable photosensitive material capable of producing images with high density and low fog. [Structure of the Invention] As a result of intensive research to achieve the above object, the present inventors have prepared, on a support, at least a photosensitive silver halide, a binder, a dye-providing substance, a reducing agent, and a compound represented by the following general formula (1). It has been found that the above objects of the present invention can be achieved by a heat-developable photosensitive material having a photographic constituent layer containing a compound. General formula (1) A-(B-) _o C In the formula, A represents a coupler residue, B is a divalent bonding group, and one bond is bonded to the active site of the coupler residue represented by A. are doing. C represents a development accelerator residue that releases the development accelerator during thermal development, and n represents 0 or 1. [Specific structure of the invention] In the general formula (1), A represents a coupler residue, and the coupler residue represented by A is as follows:
Examples include groups represented by the following general formulas (2) to (11). In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an aryl group. Sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group,
It represents an amino group, an alkoxy group, an aryloxy group, a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxyl group, a sulfo group, or a heterocyclic residue, which can further be a hydroxyl group, a carboxy group, a sulfo group, an alkoxy group, a cyano group. , a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like. Furthermore, one of these substituents (R ₁ R ₂ , R ₃ and R ₄ ) is a compound represented by the general formula (1) that releases a development accelerator during thermal development (hereinafter referred to as the compound of the present invention). It is preferable that the ballast group is substituted with various ballast groups in order to improve the immobility of the compound (referred to as compound), and the ballast group has 8 or more carbon atoms (more preferably 12 carbon atoms) depending on the form of the photosensitive material used. above), or a hydrophilic group such as a sulfo group or a carboxy group, and a group having both 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group; Mention may be made of polymer chains. In the general formula (1), B represents a divalent bonding group, and the divalent bonding group represented by B is as follows:
-S-, -O-, -NHCO-, -NHSO ₂ -, -
Examples include SO ₂ NH-, -NH-, -OCO-, -SCO-, and the like. In the general formula (1), C represents a development accelerator residue that releases a development accelerator during thermal development;
The development accelerator residue represented by is preferably a residue of a compound that adsorbs or dissolves silver ions during thermal development, or a residue of a compound that reacts with silver ions (oxidation-reduction reaction), particularly preferably a nitrogen-containing heterocycle. Examples include groups represented by the following general formula. In the above general formulas (12) to (29), D represents an oxygen atom or a sulfur atom, and R ₅ , R ₆ and R ₇ are
Each hydrogen atom, halogen atom, alkyl group, aralkyl group, alkenyl group, aryl group, acyl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, amino group, cyano group,
It represents a hydroxyl group, a nitro group, a carboxy group, a sulfo group, an alkoxycarbonyl group, a carbamoyl group, or a sulfamoyl group, and these groups further represent an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, a carboxy group, a sulfo group, a cyano group, an acyl group. , a carbamoyl group, or a sulfamoyl group. Further, when R ₅ and R ₆ are adjacent to each other, they may be bonded to each other to form a ring (eg, an aromatic ring, a carbocycle, an aliphatic carbocycle, or a heterocycle). Other examples of development accelerator residues that release a development accelerator during thermal development of the present invention include p-phenylenediamine, p-aminophenol, hydroquinone, 1-phenyl-3-pyrazolidinone, ascorbic acid, It is a residue of a compound having reducing properties such as hydrazine, hydrazide, and hydrazone. The amount of the compound of the present invention added is preferably 0.005 mol to 1 mol (more preferably 0.05 to 0.2 mol) per 1 mol of the dye-providing substance. The compound of the present invention undergoes a coupling reaction with the oxidized form of the reducing agent that is generated imagewise when the photothermographic material is imagewise exposed and thermally developed.
Releases development accelerator imagewise. Development is thus promoted imagewise, sensitivity and image density are increased without increased fog, and the objectives of the invention are achieved. Typical specific examples of the compounds of the present invention are shown below. The compounds of the present invention are generally synthesized as follows. (1) Synthesis of the coupler core and the development accelerator of the present invention (2) A leaving group (such as a halogen atom) or a group having a leaving group is introduced into the active site of the coupler (or the development accelerator). (3) Reacting the development accelerator of the present invention with a compound having a leaving group at the active site, or the coupler having a nucleophilic group at the active site and the development accelerator of the present invention having a leaving group in the presence of a base. . (4) Performing a polymerization reaction (in the case of polymers) Specific synthesis examples of the compounds of the present invention will be shown below. Synthesis Example 1 Synthesis of (A-4) (1) Synthesis of Intermediate (B) 28.3 g of N-(m-nitrophenyl)-benzoylacetamide was suspended in 400 ml of chloroform, and 5.5 ml of bromine was added at 5°C or below. Add 80 ml of chloroform solution dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, washed three times with 100 ml of water, and the chloroform solution was dried over magnesium sulfate. This solution was filtered and concentrated to obtain 36 g of bromine compound. 36g of this bromine compound and 20g of sodium salt of 1-phenyl-5-thiohydroxytetrazolone were added.
It was dissolved in 100 ml of dimethylformamide and stirred at room temperature for 1 hour. This solution was added to 300 g of water, and the precipitated solid was filtered to obtain 29 g of intermediate (B). (2) Synthesis of target product 23 g of intermediate (B) and 17.8 g of tin were dispersed in 300 ml of acetone, and 37.5 ml of concentrated hydrochloric acid was added dropwise while stirring. After dropping, stir for another hour and add 300ml.
of water was added, neutralized with sodium carbonate, filtered, and the filtrate was extracted with ethyl acetate. This extract was dried over sodium sulfate and concentrated to obtain 18.5 g of amine. Add 18.5g of this amine to 140ml of acetonitrile.
and pyridine, and a mixture of 5.6 ml of methacrylic acid chloride and 12 ml of acetonitrile was added dropwise while cooling to below 10°C. After dropping, stir for another 30 minutes and add 5% hydrochloric acid water.
The precipitated solid was filtered and dried to obtain 18.9 g of monomer (A-4). 18g of this monomer and 12g of butyl acrylate
Dissolve in 150ml of dioxane and heat at 80℃ under nitrogen stream.
azobisisobutyronitrile by heating to 1.2
g and stirred at 82-84°C for 3 hours. This solution was slowly added to the water in Step 1, and the precipitated solid was filtered and dried to obtain 28 g of the target product (A-4). As mentioned above, since the compound of the present invention involves a coupling reaction with an oxidized form of a reducing agent, the dye-serving substance used in the present invention is preferably a compound that forms a diffusible dye through a coupling reaction. Even when a substance is not used, the development accelerating effect of the present invention can be exhibited by using a reducing agent whose oxidant can couple with the compound of the present invention. Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on its reaction form, negative-acting dye-donors that act in a positive function (i.e.
A positive dye-donor acting on a negative function (i.e., a positive dye image when using a negative-working silver halide) can be classified as Negative dye-donating substances are further classified as follows.

[Table] Cut-off ring color Cut-off ring color
Elementary-emitting compound Elementary-forming compound Each dye-donating substance will be further explained. Examples of the reducible dye-releasing compound include compounds represented by general formula (30). General formula (30) Car-NHSO ₂ -Y In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of photosensitive silver halide and/or organic silver salt used as necessary. ), and Y is a diffusible dye residue. Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840, JP-A-58-116537, and JP-A-59.
−60434, No. 59-65839, No. 59-71046, No.
No. 59-87450, No. 59-88730, No. 59-123837,
They are described in the specifications of No. 59-165054 and No. 59-165055, and include, for example, the following compounds. Exemplary dye-donor substances Examples of other reducible dye-releasing compounds include compounds represented by general formula (31). General formula (31) In the formula, A ₁ and A ₂ each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye has the same meaning as Dye shown in general formula (30). Specific examples of the above compounds are shown in JP-A-59-124329. Examples of coupling dye-releasing compounds include compounds represented by general formula (32). General formula (32) Cp ₁ - (J-) _o1 Dye In the formula, Cp ₁ is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, J is a divalent bonding group, and the bond between Cp ₁ and J is cleaved by reaction with the oxidized form of the reducing agent. n ₁ represents 0 or 1, and Dye has the same meaning as defined in general formula (30). In addition, Cp ₁ is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms ( (more preferably 12 or more) organic groups, or hydrophilic groups such as sulfo groups and carboxy groups, or 8 or more (more preferably 12 or more) carbon atoms and hydrophilic groups such as sulfo groups and carboxy groups. It is a group that both have. Another particularly preferred ballast group can include polymer chains. Specific examples of the compound represented by the above general formula (32) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-
They are described in the specifications of No. 224883, No. 59-159159, and Japanese Patent Application No. 59-104901, and include, for example, the following compounds. Exemplary dye-donor substances Examples of the coupling dye-forming compound include compounds represented by general formula (33). General formula (33) Cp ₂ -(X-)-(Q) In the formula, Cp ₂ is an organic group (so-called coupler) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. residue), and X
represents a divalent bonding group, and Q represents a ballast group. The coupler residue represented by Cp ₂ preferably has a molecular weight of 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed. In addition, the ballast group is preferably the same as the ballast group defined in general formula (32), particularly 8
A group having at least 12 carbon atoms (more preferably 12 or more) and a hydrophilic group such as a sulfo group or a carboxy group is preferable, and a polymer chain is more preferable. The coupling dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (34). General formula (34) Cp ₂ -(X-)-(Y-) _l -(Z-)-(L) In the formula, Cp ₂ X has the same meaning as defined in general formula (33), and Y represents an alkylene group, an arylene group, or an aralkylene group, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. Specific examples of coupling dye-forming compounds represented by general formulas (33) and (34) include JP-A-59
-124339, 59-181345, patent application 1982-109293
No. 59-179657, No. 59-181604, No. 59-
They are described in the specifications of No. 182506 and No. 59-182507, and include, for example, the following compounds. Exemplary dye-donor substances In more detail, the coupler residue defined by Cp ₁ or Cp ₂ in the above general formulas (32), (33) and (34) is preferably a group represented by the following general formula. In the formula, R ₈ , R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarboxy group, an aryloxycarbonyl group, an alkylsulfonyl group, or an aryl group. Sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group,
It represents an amino group, an alkoxy group, an aryloxy group, a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxyl group, a sulfo group, or a heterocyclic residue, which can further be a hydroxyl group, a carboxy group, a sulfo group, an alkoxy group, a cyano group. , a nitro group, an alkyl group, an aryl group, an aryloxy group, an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like. These substituents are selected depending on the purpose of Cp ₁ and Cp ₂ , and as mentioned above, in Cp ₁ , one of the substituents is preferably a ballast group, and in Cp ₂ , it is preferable to In order to increase the molecular weight, the substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less. Examples of positive dye-providing substances include oxidizable dye-releasing compounds represented by the following general formula (45). In the formula, W ₁ represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring), R ₁₂ represents an alkyl group or a hydrogen atom, and E represents

[Formula] (In the formula, R ₁₃ represents an alkyl group or a hydrogen atom, and R ₁₄ represents an oxygen atom or

Represents [formula]. ) or -SO ₂ -, r represents 0 or 1, Dye is the general formula (30)
It has the same meaning as defined in . Specific examples of this compound are described in the specifications of JP-A-59-166954 and JP-A-59-154445, and include the following compounds. Exemplary dye-donating substances Another positive dye-providing substance is a compound represented by the following general formula (46), which loses its dye-releasing ability when oxidized. In the formula, W ₂ represents a group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R ₁₂ , E, and Dye are defined in general formula (45). It is synonymous with thing. Specific examples of this compound are described in the specifications of JP-A-59-124329 and JP-A-59-154445, and include the following compounds. Exemplary dye-donating substances Still another positive dye-providing substance includes a compound represented by the following general formula (47). In the above formula, W ₂ , R ₁₂ and Dye are the general formula (46)
It has the same meaning as defined in . Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds. Exemplary dye-donating substances The above general formulas (30), (31), (32), (45), (46
),
The residues of the diffusible dye represented by Dye in (47) will be described in further detail. Due to the diffusivity of the dye, the residue of the diffusible dye has a molecular weight of 800 or less,
More preferably, it is 600 or less,
Examples include residues of azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like. These dye residues may be in a temporary short-waveform form that allows multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in
The chelatable dye residues described in Japanese Patent Nos. 48765 and 59-124337 are also preferred monomorphs. These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited, and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers. You can decide accordingly, but for example, the usage amount is 1 m ²
It can be used in an amount of 0.005g to 50g, preferably 0.1g to 10g. The dye-providing substance used in the present invention can be incorporated into the photographic constituent layer of the heat-developable color light-sensitive material using any method. tricresyl phosphate, etc.), followed by long-wave dispersion, or dissolved in an alkaline aqueous solution (e.g., 10% sodium hydroxide aqueous solution, etc.), and then dissolved in mineral acid (e.g., hydrochloric acid or nitric acid, etc.). It can be used after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.). The heat-developable color photosensitive material of the present invention contains a photosensitive silver halide together with the compound of the present invention and the dye-providing substance. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used 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. Light-sensitive silver halide emulsions containing light-sensitive silver halides prepared accordingly give favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grain or fine grain, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.01 μm to about 1.5 μm. It is approximately 0.5 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, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part 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 represents I,
n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. As a metal atom,
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,
Examples include iron, 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 ,
( _NH4 ) _{3RhCl6 ,} ( _NH4 ) _{3RhBr6 ,} etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzyl quaternary ammonium halides such as ammonium bromide, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenation Hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-
Bromophthalic acid imide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzene sulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). be able to. 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 g per m ² per layer.
It is preferable that it is ~50g, more preferably,
The amount is 0.1g to 10g. 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. You can also. Further, the same color photosensitive layer can be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. 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 pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. 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, oxazolidione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as US Pat. No. 2,933,390,
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these dyes added is 1.times.10.sup. ^-4 mol to 1 mol per mol of silver halide or silver halide-forming component. More preferably, 1×10 ⁻⁴ mol to 1×
10 ^-1 mole. In the heat-developable color photosensitive material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability. Examples of organic silver salts used in the heat-developable color photosensitive material of the present invention include Japanese Patent Publication Nos. 43-4921 and 44-
No. 26582, No. 45-18416, No. 45-12700, No. 45
-22185, JP-A-49-52626, JP-A-52-31728,
No. 52-137321, No. 52-141222, No. 53-36224
No. 3330633, US Patent No. 3794496, and US Patent No. 4105451.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, arachidone as described in the specifications of No. 4123274, No. 4168980, etc. acid silver,
Silver aromatic carboxylates such as silver behenate, silver α-(1-phenyltetrazolethio)acetate, etc., such as silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582,
45-12700, 45-18416, 45-22185,
JP-A-52-31728, JP-A-52-137321, JP-A-58
Silver salts of imino groups such as those described in publications such as No. 118638 and No. 58-118639, such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, and silver 5-methoxybenzotriazole. Silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver,
1,2,4-triazole silver, 1H-tetrazole silver, 3-amino-5-benzylthio-1,2,
Silver 4-triazole, silver saccharin, silver phthalazinone, silver phthalimide, etc. Silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole,
2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver, 4-hydroxy-6-methyl-1,3,
Examples include 3a,7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of benzotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred. The organic silver salts used in the present invention may be used alone or in combination of two or more, and isolated ones may be used by dispersing them in a binder by appropriate means, or they may be used in a suitable form. The silver salt may be prepared in a binder and used as is without isolation. The amount of the organic silver salt used is 1 photosensitive silver halide.
Preferably, it is 0.01 to 500 mol per mol,
More preferably, it is 0.1 mol to 100 mol. As the reducing agent used in the heat-developable color photosensitive material of the present invention, those commonly used in the field of heat-developable color photosensitive materials can be used, such as those disclosed in U.S. Pat. Specification, RD No. 12146, RD No. 15108, RD No.
15127 and p described in Japanese Patent Application Laid-Open No. 56-27132, etc.
- phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenolic type and sulfonamide phenolic type developing agents,
Further examples include hydrazone color developing agents. Further, color developing agent precursors and the like described in U.S. Pat. No. 3,342,599, U.S. Pat. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (48) described in No. In the formula, R ₁₅ and R ₁₆ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R ₁₅ and R ₁₆ represent a closed ring. May form a heterocycle. _R17 , _R18 ,
R ₁₉ and R ₂₀ each have a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number of 1 to 1, which may have a substituent.
represents an alkyl group of 30 (preferably 1 to 4),
R ₁₇ and R ₁₅ and R ₁₉ and R ₁₆ may each be closed to form a heterocycle. M is an alkali metal atom,
Represents a compound containing an ammonium group, a nitrogen-containing organic base, or a quaternary nitrogen atom. The nitrogen-containing organic base in the general formula (48) is an organic compound containing a nitrogen atom that exhibits basicity capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. Next, preferred specific examples of the reducing agent represented by the general formula (48) are shown below. The reducing agent represented by the above general formula (48) can be prepared by a known method such as Houben-Weyl, Methodender
Organischen Chemie, Band I/2, 645−
It can be synthesized according to the method described on page 703. Other reducing agents as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1′ -dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4-dimethoxy-1,1'-dihydroxy-
2,2-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-melenbis(2-hydroxy-3-tert-butyl-5
-methylphenyl)-4-methylphenol, α
-Phenyl-α,α-bis(2-hydroxy-
3,5-di-tert-butylphenyl)methane, α
-phenyl-α,α-bis(2-hydroxy-3
-tert-butyl-5-methylphenyl)methane,
1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,
5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy- 3,5
-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenyl diamines. 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 photosensitive silver halide used, the type of organic acid silver salt, and the types of other additives, but it is usually per mol of photosensitive silver halide.
It ranges from 0.01 to 1500 mol, preferably from 0.1 to 1500 mol.
It is 200 moles. Examples of the binder used in the heat-developable color photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate,
polyvinyl alcohol, polyvinylpyrrolidone,
One or a combination of two or more synthetic or natural polymeric substances such as gelatin and phthalated gelatin can be used. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in Japanese Patent Application No. 104249/1982. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including kraft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1000
~400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl imidazoles, (meth)acrylamides, and vinyl carbinols. , vinyl monomers such as vinyl alkyl ethers, etc., but it is preferable that polyvinylpyrrolidone accounts for at least 20% (weight %, same hereinafter) of the composition ratio. Preferred examples of such copolymers have a molecular weight of
5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pitgskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinylpyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05g to 50g per square ^meter per layer, preferably 0.1g to 10g.
It is g. Further, the binder is preferably used in an amount of 0.1 to 10 g, more preferably 0.25 to 4 g, per 1 g of the monomer unit of the dye-donating substance. Examples of the support used in the heat-developable color photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, photographic base paper, printing paper, baryta paper, and resin coating. Examples include a paper support such as paper, a support made of the above-mentioned synthetic plastic film provided with a reflective layer, and the like. In particular, it is preferable that various heat solvents be added to the heat-developable color photosensitive material of the present invention. The thermal solvent of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably a substance that is solid at room temperature.
Semi-solid or liquid (preferably boiling point at normal pressure)
100°C or higher, more preferably 150°C or higher) and dissolves or melts in the binder by heating, preferably urea derivatives (e.g. dimethylurea, diethylurea, phenylurea, etc.), amides. derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene glycol Examples include: For a detailed concrete example, see patent application No. 58-104249.
It is described in. These thermal solvents may be used alone or in combination of two or more. 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.
No. 3220840, No. 3531285, No. 4012260, No. 4060420, No. 4088469, No. 4207392, RD No. 15733, No. 15734, No. 15776,
Alkali release agents such as urea and guanidium trichloroacetate described in JP-A-56-130745 and JP-A-56-132332, organic acids as described in JP-A-45-12700, - as described in U.S. Pat. No. 3,667,959 CO−,−
Non-aqueous polar solvent compounds having SO ₂ -, -SO- groups, melt formers described in U.S. Patent No. 3,438,776, polyalkylene glycols described in U.S. Pat. . In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5020, No. 49
−91215, No. 49-107727, No. 50-2524, No.
No. 50-67132, No. 50-67641, No. 50-114217,
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-
No. 156525, No. 54-156526, No. 55-4060, No. 55
Publications such as -4061 and 55-32015, as well as West German Patent Nos. 2140406, 2147063, 2220618,
U.S. Patent No. 3080254, U.S. Patent No. 3847612, U.S. Patent No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazine, etc. Sangeon,
2,3-dihydro-phthalazinedione, 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., mixtures of one or more of these with imidazole compounds, and acids such as phthalic acid, naphthalic acid, or Examples include mixtures of at least one acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, JP-A-58-189628, JP-A No. 58-189628,
3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles described in Japanese Patent No. 193460 are also effective. Furthermore, as antifoggants, for example,
Special Publication No. 11113, No. 49-90118, No. 49-
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen acetamide,
N-halogenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or
Acids and their salts (e.g., sulfuric acid, lithium laurate, rosin, diterpenic 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,
Examples include compounds such as 1,2,4-triazole and phthalimide. Furthermore, thiol (preferably a thiophenol compound) compound described in JP-A-59-111636 is also effective as another antifoggant. In addition, as other anti-fogging agents,
Hydroquinone derivatives described in No. 56506 (e.g.
di-t-octylhydroquinone, dodecanylhydroquinone, etc.), hydroquinone derivatives and benzotriazole derivatives (e.g., 4-sulfobenzotriazole,
-carboxybenzotriazole, etc.) can be preferably used in combination. 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-trisulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6
-Methyltriazine, etc. 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 stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
The activator stabilizer precursor described in No. 4060420, etc. may also be contained. In addition, a water release agent such as sucrose, NH ₄ Fe (SO ₄ ) _{2.12H 2} O, etc. may be used.
Heat development may be carried out by supplying water as in No. 132332. In addition to the above-mentioned components, the heat-developable color photosensitive material of the present invention may optionally contain various components such as a spectral sensitizer, an antihalation dye, a fluorescent brightener, a hardening agent, an antistatic agent, a plasticizer, and a spreading agent. Additives, coating aids, etc. are added. The heat-developable color photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) reducing agent, (3) in the same layer.
It is preferable that the composition contains a dye-providing substance, (4) a binder, and (5) the compound of the present invention, and further contains (6) an organic silver salt if necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, two photosensitive layers may be included.
The components (1), (2), (4), (5), and (6) are contained in the photosensitive layer on one side, and the dye is provided in the layer on the other side adjacent to this photosensitive layer. Including substance (3), etc.
As long as they are in a state where they can react with each other, they may be contained separately in two or more photographic constituent layers. Further, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and may further include one or more other photosensitive layers having different color sensitivities. It may also have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and an intermediate layer. Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or Patent No.
Photosensitive materials can be prepared by various coating methods such as the hopper coating method described in No. 3681294. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. The above-mentioned components used in the photographic constituent layers of the heat-developable color light-sensitive material of the present invention are coated on a support,
The thickness of the coating is preferably 1 to 1000 μm after drying,
More preferably, it is 3 to 20 μm. After the heat-developable color photosensitive material of the present invention is subjected to imagewise exposure as it is, the temperature is usually 80°C to 200°C, preferably 120°C.
Color development can be achieved by simply heating at a temperature range of 170° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be developed at 70% before exposure.
Preheating may be performed at a temperature range of 180°C to 180°C. Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is obtained by streak exposure to radiation, including visible light. A light source commonly used for normal color printing,
For example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam, etc. can be used as the light source. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, to provide a conductive layer in the photosensitive material of the present invention or in the image receiving layer (element) for thermal transfer, and to utilize the Joule heat generated by electricity or a strong magnetic field. The heating pattern is not particularly limited;
Although it is possible to preheat the temperature in advance and then reheat it, continuously raise, lower, or repeat heating at a high temperature for a short time, or at a low temperature for a long time, or even discontinuously, it is not easy. A pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image-receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and can be used as a mordant used in dye diffusion transfer type light-sensitive materials or as described in JP-A No. 57-207250. 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. 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.
Polymers containing dialkylamino groups disclosed in U.S. Pat. No. 2,675,316; aminoguanidine derivatives disclosed in U.S. Pat. No. 2,882,156;
covalently reactive polymers as described in No. 137333;
US Patent No. 3625694, US Patent No. 3859096, British Patent No.
Mordant capable of crosslinking with gelatin etc. disclosed in No. 1277453 and No. 2011012, US Patent No. 3958995
No. 2721852 and No. 2798063; water-insoluble mordants disclosed in JP-A-50-61228; U.S. Patent No. 3788855;
West German Patent Application (OLS) No. 2843320, JP-A-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, such as those containing quaternary amino groups as described in US Pat. No. 3,709,690. Polymers containing ammonium salts include, for example, polystyrene copolymer.
In N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, the ratio of styrene and vinylbenzylammonium chloride is:
The ratio is 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. 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, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, and polyvinyl alcohol. , polyacetals such as polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorofluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylacrylamide, p-cyanophenyl group, pentachlorophenyl group, and 2, Polyacrylate with 4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl metal acrylate, 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 ed. (J.
Brandrup, EHImmergut ed.) John Wiley &
Glass transition temperature listed in Sons Publishing, 40
Synthetic polymers at temperatures above 0.degree. 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 heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane Examples include polyester, polyethylene terephthalate, polycarbonate, and vinyl chloride that can be combined with ethylene glycol. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene-glycol, 1,2
Polyethylene terephthalate using -dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective. Among these, particularly preferred are the layer made of polyvinyl chloride described in Japanese Patent Application No. 58-97907, and the layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 128600-1982. 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 by a member (for example, a film) made of the above-mentioned polymer alone (also used as an image-receiving layer support). Further, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing gelatin-branched titanium dioxide or the like 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. [Example] Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Example 1 Exemplary dye-providing substance (weight average molecular weight = 9400)
750 mg and 40 mg of the compound (A-4) of the present invention were dissolved in 2.5 cc of ethyl acetate. This solution was mixed with 3 c.c. of a 2.5% gelatin aqueous solution containing a surfactant, water was added to make 6.5 cc, and then dispersed with a homogenizer.
A dispersion of a dye-providing substance was obtained. 6.5 cc of the above dispersion was mixed with 3.5 cc of water containing 450 mg of polyvinylpyrrolidone (average molecular weight 30,000), 300 mg of 1,5-pentanediol, and polyethylene glycol (average molecular weight 300), and 0.1 ml of 10% guanidine trichloroacetic acid in ethanol was added. After adding ml and 200mg of the reducing agent (R-3), 3%
The pH was adjusted to 5.5 with citric acid. A silver iodobromide emulsion with an average grain size of 0.1 μm was added to this dispersion at a rate of 1× in terms of silver.
After adding 10 ^-3 mol (containing 85 mg of gelatin) and finishing with water to a total volume of 15 c.c., the photosensitive layer was coated onto a polyethylene terephthalate support using a wire bar so that the dry film thickness was 8 μm. did. After drying the resulting light-sensitive material, it was exposed to white light at 16,000 CMS through a step wedge. Next, the image-receiving layer surface of an image-receiving sheet on which polyvinyl chloride as an image-receiving layer material was separately coated on baryta paper and the coated surface of the exposed photosensitive material were superimposed and thermally developed at 150° C. for 1 minute to form an image-receiving sheet. was peeled off to obtain a yellow transferred image on the image-receiving sheet. Table 1 shows the maximum reflection density (Dmax) and fog (Dmin) of the obtained transferred image. Comparative Example 1 The same photosensitive material as in Example 1 was prepared except that the compound (A-4) of the present invention was removed from the photosensitive material of Example 1, and the same heat development as in Example 1 was performed. The results are shown in Table-1.

[Table] From the results in Table 1, it can be seen that the sample of the present invention has almost no change in Dmin and a significant increase in Dmax compared to the comparative sample. Example 2 [Preparation of silver 4-sulfobenzotriazole] 24 g of 4-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 at room temperature for 1 hour and then made up to 400 ml with water to prepare a 4-sulfobenzotriazole silver solution containing 20% excess of 4-sulfobenzotriazole. [Preparation of photosensitive material] 450 mg of the same dye-providing substance as in Example 1, 40 mg of the compound (A-4) of the present invention, and 30 mg of 1,4-dioctylhydroquinone were dissolved in 2.5 cc of ethyl acetate. This solution was mixed with 3 cc of a 2.5% aqueous gelatin solution containing a surfactant, water was added to make 6.5 cc, and the mixture was dispersed with a homogenizer to obtain a dispersion of the dye-providing substance. 4 ml of the above 4-sulfobenzotriazole silver solution and 6 c.c.
30000) 450mg, Pentaerythritol 120mg, 1,
After adding 420 mg of 5-pentanediol and 200 mg of the same reducing agent (R-3) used in Example 1,
The pH was adjusted to 5.5 with 3% citric acid. A silver iodobromide emulsion with an average particle size of 0.05 μm was added to this dispersion in an amount of 3×10 ⁻⁴ mol (containing 75 mg of gelatin) in terms of silver, and water was added to make a final volume of 14 ml. A photosensitive layer was applied using a wire bar so that the dry film thickness was 8 μm. After drying the resulting photosensitive material, it was exposed to white light at 32,000 CMS through a step wedge, and then thermally developed on the same image-receiving sheet as in Example 1 under the same conditions to obtain a yellow transferred image on the image-receiving sheet. Maximum reflection density (Dmax) of the obtained transferred image
and fog (Dmin) are shown in Table 2. Example 3 In Example 2, the same photosensitive material as in Example 2 was prepared, except that the amount of the compound of the present invention added and the compound were changed as shown in Table 2. Development was performed to obtain a yellow transferred image on the image receiving sheet. The results are shown in Table-2.

【table】

[Table] As is clear from the results in Table 2, the samples using the compound of the present invention had a lower
It can be seen that Dmin hardly changes, but Dmax increases significantly, indicating a high concentration. Example 4 The same photosensitive material as in Example 2 was prepared except that the amounts of the dye-providing substance, the compound of the present invention (A-4), and the reducing agent were changed as shown in Table 3. The same exposure and thermal development as in Example 2 were carried out to obtain a transferred image on an image-receiving sheet. Table 3 shows the results.
Shown below. Furthermore, 0.1 ml of a 10% guanidine trichloroacetic acid solution in ethanol is added to the light-sensitive materials containing dye-donating substances (1) and (2), and in the case of these light-sensitive materials, the following image-receiving paper is used. I used something. 10 g of a copolymer of methyl acrylate and vinylbenzylammonium chloride (composition ratio 1:1)
100ml of 10% gelatin solution dissolved in 100ml of water
mixed with. This liquid was coated onto baryta paper to a dry film thickness of 15 μm to obtain image receiving paper.

【table】

[Table] As is clear from the results in Table 3, the samples using the compound of the present invention were more effective than the samples not using the compound of the present invention, regardless of which dye-providing substance was used.
It can be seen that Dmin has hardly changed and Dmax has increased significantly.

Claims (1)

[Scope of Claims] 1. A photographic constituent layer containing at least a photosensitive silver halide, a binder, a dye-providing substance, a reducing agent, and a compound represented by the following general formula (1) on a support. A heat-developable photosensitive material. General formula (1) A-(B-) _o C In the formula, A represents a coupler residue, B is a divalent bonding group, and one bond is bonded to the active site of the coupler residue represented by A. are doing. C represents a development accelerator residue that releases the development accelerator during thermal development, and n represents 0 or 1.