JPH0146055B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material that provides a high maximum density and less fog. [Prior Art] A method in which the development step for obtaining a color image is performed by dry heat treatment has many advantages over the conventional wet method in terms of processing time, cost, and concerns about pollution. Therefore, many proposals regarding such heat-developable color photosensitive materials have been made in recent years, for example, JP-A-57-179840;
No. 186744, No. 57-198438, No. 57-207250, No.
No. 58-40551, No. 58-58543, No. 58-79247,
Patent application No. 57-122596, No. 57-132884, No. 57-
No. 179236, No. 57-229671, No. 57-229674, No.
No. 57-229675, No. 58-33363, No. 58-33364,
No. 58-34083, JP-A No. 58-116537, No. 58-
There are No. 123533, No. 58-149046, No. 58-149047, etc. The basic composition of these previously proposed heat-developable color photosensitive materials consists of a photosensitive element and an image-receiving element, and the photosensitive element basically consists of an organic silver salt, a photosensitive silver halide, a developer (reducing agent), and a dye donor. It consists of a compound and a binder. That is, optical information is given to the photosensitive silver halide by image exposure,
In thermal development, dissolution physical development according to optical information is performed between an organic silver salt and a photosensitive silver halide under the action of a developer, and the developer that has acted or has not acted is converted into a dye-providing compound. Upon reaction, a dye that forms an image is released or formed. The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image. In thermal development, the reaction proceeds at high temperatures, resulting in unpredictable thermal fog.
The mechanism for this is thought to be the generation of fog nuclei on the surface of photosensitive silver halide or organic silver salt, the influence of thermal decomposition products, etc., but it is not clear. On the other hand, there are many proposals as thermal fog preventive agents. For example, the mercury compound of US Patent No. 3,589,903, the N-halogeno compound of West German Patent No. 2,402,161,
Peroxide of No. 2500508, sulfur compound of No. 2617907, palladium compound of U.S. Patent No. 4102312, sulfinic acids of Japanese Patent Publication No. 53-28417, Mercaptotriazole of Research Disclosure No. 169077, No. 169079, U.S. Patent No. 4137079 1, 2,
There are 4-triazole and the like. However, these thermal fog preventive agents are extremely harmful to the human body, have a small preventive effect, or even if they have a preventive effect, cause a decrease in the maximum density, so that no effective antifoggant has been found. [Object of the present invention] Accordingly, an object of the present invention is to provide a heat-developable color photosensitive material that causes less fog.
Another object of the present invention is to provide a heat-developable color photosensitive material that provides a high maximum density and less fog. [Structure of the Invention] The object of the present invention is to provide at least (a) a photosensitive silver halide, (b) an organic silver salt, (c) a developer, (d) a dye-providing compound, and (e) a binder on a support. A heat-developable color photosensitive material having at least one heat-developable photosensitive layer, characterized in that at least one of the heat-developable photosensitive layers contains a compound represented by the following general formula (1). achieved by. In the above formula, R ₆ , R ₇ and R ₈ are each a hydrogen atom,
Halogen atom (preferably chlorine atom, bromine atom,
iodine atom), alkyl group (preferably 1 to 1 carbon atoms),
24 alkyl groups, such as methyl, ethyl,
Groups such as butyl, t-amyl, t-octyl, n-dodecyl, n-pentadecyl, and cyclohexyl can be mentioned, and examples of alkyl groups substituted with aryl groups, such as phenyl groups, include benzyl groups and phenethyl groups. ), substituted or unsubstituted aryl groups (e.g. phenyl group,
naphthyl group, tolyl group, mesityl group), acyl group (e.g. acetyl group, tetradecanoyl group, pivaloyl group, substituted or unsubstituted benzoyl group),
Alkyloxycarbonyl groups (e.g. methoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group, α
-naphthoxycarbonyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), alkylamino group (e.g. ethylamino group, t-octylamino group), arylamino group (e.g. anilino group), groups, as well as halogen atoms, alkyl groups,
anilino group substituted with a substituent such as an amide group or an imido group), a carbamoyl group (e.g., substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecyl Carbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, specifically 2,4-di-
t-phenoxybutyl-carbamoyl group, substituted or unsubstituted phenylcarbamoyl group, specifically 2-dodecyloxyphenylcarbamoyl group, etc.), substituted or unsubstituted acylamino group (e.g. n-butylamide group, laurylamide group, an optionally substituted β-phenoxyethylamide group,
phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamide ethylamide group, β-methoxyethylamide group, etc.), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy group, ethoxy group) , octadecyloxy group, etc.), sulfamoyl group (e.g., methylsulfamoyl group, n-dodecylsulfamoyl group, substituted or unsubstituted phenylsulfamoyl group, specifically dodecyl phenylsulfamoyl group, etc.) , an alkylsulfonylamino group or an arylsulfonylamino group (for example, a methylsulfonylamino group, a tolylsulfonylamino group), a sulfo group, a carboxy group or a hydroxyl group. R ₅ and R ₉ each represent an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, such as a methyl group, a butyl group, a lauroyl group, a heptadecyl group, etc.). However, the total number of carbon atoms in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is 8 or more. Specific examples of the compound represented by the general formula (1) of the present invention (hereinafter referred to as the compound of the present invention) are shown below, but the present invention is not limited thereto. Synthesis of these compounds is METHODEN DER
ORGANISCHEN CHEMIE (HOUBEN−
WEYL）BAND V1/1C PHENOLE Teil l
(GEORG THIEME VERLAG STUTTGART
It can be carried out according to the method described in 1976). The amount of the compound of the present invention added is usually 0.001 mol to 0.5 mol per mol of silver contained in the heat-developable photosensitive layer.
mol, preferably in the range of 0.005 mol to 0.2 mol. The method of adding the compound of the present invention is not particularly limited, but it is preferably added by dissolving it in a high boiling point solvent, or preferably adding the compound having a hydrophilic group by dissolving it in an alkaline solution. The compounds of the present invention work most effectively in combination with dye-providing compounds in high-boiling solvents such as tricresyl phosphate, dioctyl phthalate,
Dissolved in N,N-diethyl laurylamide etc.
This is the case when it is added as an oil-in-water type dispersion. In compounds other than the present invention, for example, general formula (1),
If the total number of carbon atoms in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is less than 8, fogging will increase, which is contrary to the purpose of the present invention. Furthermore, if the total number of carbon atoms exceeds 30, synthesis becomes difficult and the antifogging effect is also reduced, so it is usually 8 or more and 30 or less, preferably 8 or more and 24 or less. Furthermore, the compound of the present invention can also be used in combination with a quinone compound as shown in JP-A-55-161238. The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., and the grain size is usually 0.01 μm to
1.0 μm, preferably 0.05 μm to 0.5 μm. The amount of photosensitive silver halide is usually 0.001 mol to 100 mol, preferably 0.05 mol to 10 mol, per mol of organic silver salt.
It is in the molar range. The shape of the silver halide is not particularly limited and may be a regular tetrahedron, a regular octahedron, a tetradecahedron, etc., but one having at least (1,1,1) faces is preferred. Alternatively, the particles may be of a core-shell type in which the halogen composition is different between the inside and outside of the particle. The photosensitive silver halide used in the present invention is preferably chemically sensitized. In addition to sulfur sensitization and selenium sensitization, sensitization using compounds such as gold, platinum, and palladium may be combined. Furthermore, it is preferable that the material is spectral sensitized using a spectral sensitizing dye such as that used in ordinary silver halide color light-sensitive materials. Further, the photosensitive silver halide is preferably dispersed in various hydrophilic colloids including gelatin and gelatin derivatives. As the photosensitive silver halide used in the present invention, the photosensitive silver halide described in the patent specification filed by the present inventors on December 28, 1983 is particularly preferred. Examples of organic silver salts used in the heat-developable color photosensitive material of the present invention include Japanese Patent Publication No. 43-4924 and Japanese Patent Publication No. 44-4924;
No. 26582, No. 45-18416, No. 45-12700, No. 45
-22185 and JP-A-49-52626, JP-A No. 52-31728
No. 52-13731, No. 52-141222, No. 53-
No. 36224, Publications No. 53-37610, U.S. Patent No.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc., described in specifications such as No. 3330633 and No. 4168980, etc. Silver aromatic carboxylates, such as silver benzoate, silver phthalate, silver salts having imino groups, such as silver benzotriazole, silver saccharin, silver phthalazinonic acid, silver phthalimide, and silver salts of compounds having mercapto or thione groups, such as 2-mercaptobenzoxazole silver, mercaptooxadiazole silver,
Silver mercaptobenzothiazole, silver 2-mercaptopenzimidazole, silver 3-mercaptophenyl-1,2,4-triazole, and as others 4-hydroxy-6-methyl-1,3,3a,7
-tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver, and the like. Also, Research Disclosure (RD) 16966, 16907, British Patent No. 1,590,
Silver compounds such as those described in No. 956 and No. 1,590,957 can also be used. Among these, silver salts having an imino group such as silver salts of benzotriazole are preferable, and examples of silver salts of benzotriazole include alkyl-substituted silver benzotriazoles such as silver methylbenzotriazole, silver bromobenzotriazole, silver chlorobenzotriazole, etc. Halogen-substituted benzotriazole silver such as silver, amide-substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and compounds described in British Patent Nos. 1590956 and 1590957, such as N-[6- Chloro-4
-N(3,5-dichloro-4-hydroxyphenyl)imino-1-oxo-5-methyl-2,5-
cyclohexadien-2-yl]-5-carbamoylbenzotriazole silver salt, 2-benzotriazol-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. Particularly useful organic silver salts in the present invention are JP-A-58
It has a hydrophilic group as shown in No.-118638. 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 organic silver salt used in the present invention may be isolated and used by dispersing it in a binder for a photosensitive layer by an appropriate means, or the silver salt may be prepared in a binder for a photosensitive layer, It may be used as is without isolation. The amount of the organic silver salt used is usually per 1 m ² of support.
The amount is 0.05g to 10.0g, preferably 0.2g to 5.0g. Examples of the developer used in the heat-developable color photosensitive material of the present invention include those described in U.S. Pat. No. 3,531,286, U.S. Pat.
RD12146, 15108, 15127 and JP-A-1989-
p-phenylenediamine type and p-aminophenol type developing agents, phosfluoramide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents described in JP-A No. 57-186744. , patent application 1987-122596
No. 57-160698, No. 57-126054, No. 58-
Thermal transferable dye-providing compounds described in No. 33363 and No. 58-33364 can be advantageously used. In this case, diffusible dyes are released or formed by oxidative coupling of the developer and these thermally transferable dye-providing compounds. Also US Patent No. 3342599
No. 3719492, Japanese Unexamined Patent Publication No. 135628, No. 53, No. 54
Color developing agent precursors described in No. 79035 and the like can also be advantageously used. In the present invention, a sulfamic acid type developer as shown in JP-A-56-146133 is particularly effective. Other methods include, for example, JP-A-57-
No. 179840, No. 57-102487, Patent application No. 179-229648
No. 57-229672, No. 57-225928, etc.
It is not necessarily necessary to use the above-mentioned developer, and the following developer can be used. That is, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-t
-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-toluenesulfonamido)phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone,
t-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
-t-butyl-5-methylphenyl)methane,
1,1-bis(2-hydroxy-3,5-di-t
-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-t-butyl-5-methylphenyl)-4-methylphenol-α-phenyl-α,α-bis(2-hydroxy-3,5-
di-t-butylphenyl)methane, α-phenyl-α,α-bis(2-hydroxy-3-t-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy-3,5-dimethylphenyl) enyl)−
2-methylpropane, 1,1,5,5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)
Propane, 2,2-bis(4-hydroxy-3-
methyl-5-t-butylphenyl)propane,
2,2-bis(4-hydroxy-3,5-di-t
-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. These developers can be used alone or in combination of two or more. The amount of developer used depends on the type of organic silver salt used, the type of photosensitive silver halide, and the types of other additives, etc.
Usually, the amount is in the range of 0.05 mol to 10 mol, preferably 0.1 mol to 3 mol, per mol of organic silver salt. Examples of dye-providing compounds that can be used in the heat-developable color photosensitive material of the present invention include, for example, JP-A-57
−179840, No. 57-186744, No. 58-116537,
No. 57-123533, No. 57-149046, No. 59-12431
No., Patent Application No. 57-160698, No. 57-205447, No. 57
−224883, No. 57-224884, No. 57-229671,
No. 57-229647, No. 57-225929, No. 58-33363
Examples include dye-providing compounds that can be used in diffusion transfer type heat-developable photosensitive materials as described in No. 1, No. 58-33364, No. 58-34083, and the like. The dye-providing compound preferably used in the present invention is a dye-forming compound and can be represented by the following general formula (). General formula () Cp-X In the formula, Cp represents a coupler residue excluding the hydrogen atom at the active position, and Cp contains a hydrophilic group such as a sulfo group or a carboxy group, or a hydrophilic group other than the active position. It is a coupler residue that does not have a group. X represents a group that can be separated from the coupler during the coupling reaction, and further has one or more hydrophilic groups such as a sulfo group or a carboxy group, or a group containing these hydrophilic groups, and preferably has a straight chain or branched alkyl group having 8 or more carbon atoms. Examples of the coupler residue represented by Cp include those represented by the following general formulas () to (). In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, or an iodine atom), or an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms). Yes, such as methyl, ethyl, butyl, t-octyl, n-dodecyl, n
Examples include groups such as -pentadecyl and cyclohexyl, but also benzyl groups and phenethyl groups may be used as alkyl groups substituted with aryl groups, such as phenyl groups), and substituted or unsubstituted aryl groups (such as phenyl groups). group, naphthyl group, tolyl group, mesityl group), acyl group (e.g. acetyl group, tetradecanoyl group, pivaloyl group, substituted or unsubstituted benzoyl group), alkyloxycarbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group) ), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group, α-
naphthoxycarbonyl group), alkylsulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), carbamoyl group (e.g. substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecyl group) carbamoyl group, N-methyl-N-dodecylcarbamoyl group,
An optionally substituted phenoxyalkylcarbamoyl group, specifically a 2,4-di-t-phenoxybutyl-carbamoyl group, a substituted or unsubstituted phenylcarbamoyl group, specifically 2-dodecyloxyphenylcarbamoyl group), substituted or unsubstituted acylamino group (e.g. n-butylamide group, laurylamide group, optionally substituted β
-Phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamidoethylamide group, β-
methoxyethylamide group), an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, an octadecyloxy group),
Sulfamoyl group (e.g. methylsulfamoyl group, n-dodecylsulfamoyl group, substituted or unsubstituted phenylsulfamoyl group, specifically dodecylphenylsulfamoyl group), alkylsulfonylamino group or arylsulfonyl group Amino group (e.g. methylsulfonylamino group,
(tolylsulfonylamino group) or hydroxyl group. Further, R ₁ and R ₂ may be combined with each other to form a saturated or unsaturated 5- to 6-membered ring. R ₅ is an alkyl group (preferably 1 to 1 carbon atoms)
24 alkyl groups (e.g. methyl, butyl, heptadecyl), alkoxy groups (preferably alkoxy groups having 1 to 18 carbon atoms, e.g. methoxy, ethoxy, octadecyloxy), arylamino groups (e.g. anilino, Furthermore, halogen atoms, alkyl groups, amide groups, anilino groups substituted with substituents such as imido groups), substituted or unsubstituted alkylamido groups (e.g. laurylamide, optionally substituted phenoxyacetamide, enoxybutanamide group), a substituted or unsubstituted arylamide group (for example, a benzamide group, and a benzamide group further substituted with a halogen atom, an alkyl group, an alkoxy group, an amide group, etc.), and the like. Furthermore, R ₆ , R ₇ and R ₈ are a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably an alkyl group having 1 to 2 carbon atoms, such as a methyl group or an ethyl group) , substituted or unsubstituted alkylamide groups (e.g. laurylamide group, optionally substituted phenoxyalkylamide group, e.g. alkyl-substituted phenoxyacetamide group), substituted or unsubstituted arylamide group (e.g. benzoylamide group) ) etc. Next, R ₉ is an alkyl group (preferably 1 carbon number
~8 alkyl groups (e.g. methyl group, butyl group,
octyl group), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, methoxyphenyl group), etc. Furthermore, R ₁₀ represents an arylamino group (for example, an anilino group, an anilino group further substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imido group, etc.). Moreover, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are
It has the same meaning as the group represented by R ₁ and R ₂ above. Typical specific examples of the dye-providing compound represented by the general formula () include the following compounds. [Exemplary dye-providing compound] The dye-providing compound used in the present invention varies depending on the photothermographic composition, coating conditions, processing method, etc., but approximately 0.01 mol to 10 mol per mol of organic silver salt.
Used in a mole range, preferably 0.1 mole to 2.0 mole
It is a mole. In order to incorporate the dye-providing compound used in the present invention into the heat-developable photosensitive layer, it can be dissolved in a high boiling point solvent as described in US Pat. No. 2,322,027 relating to a coupler dispersion method. Furthermore, in the above dispersion method, the dye-providing compound can be dissolved and contained in the heat-developable photosensitive layer by using a low boiling point solvent in combination with the high boiling point solvent, if necessary. Examples of the above-mentioned high boiling point solvents include di-n-butyl phthalate, tricresyl phosphate, di-octyl phthalate, n-nonylphenol, etc., and examples of low boiling point solvents include methyl acetate, butyl propionate, Known examples include cyclohexanol and diethylene glycol monoacetate. Even if these solvents are used alone,
The 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 compound, 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. Fissure dispersion refers to dissolving and dispersing a dye-providing substance having a hydrophilic component and a hydrophobic component in the same molecule in an alkaline aqueous 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. The above-mentioned Fissure dispersion is also called Agfa dispersion, and is described in British Patent No. 45555 and British Patent No. 45555.
The technical contents described in No. 465823, No. 29897, etc. can be referred to. The binder used in the heat-developable photosensitive layer of the heat-developable color photosensitive material of the present invention may be either a hydrophobic binder or a hydrophilic binder, but a hydrophilic binder is preferred. When a hydrophilic binder is used, a hydrophobic binder may also be used in part. The hydrophilic binder in the present invention refers to one that is soluble in water or a mixture of water and an organic solvent (a solvent that is miscible with water). Examples include proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, and useful polymers such as polyvinyl acetals (preferably with a degree of acetalization below 20%, e.g. polyvinyl butyral). , polyacrylamide, polyvinylpyrrolidone, ethylcellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), etc., but are not limited to these. If necessary, two or more types may be used in combination. In particular, it is preferable to use a mixture of gelatin or a gelatin derivative and an organic polymeric substance such as polyvinylpyrrolidone or polyvinyl alcohol. The amount of the binder is in a weight ratio of 1/10 to 10 parts, preferably 1/4 to 4 parts, per 1 part (by weight) of the organic silver salt for each photosensitive layer. The binder used in each layer (hydrophilic colloid) other than the heat-developable photosensitive layer of the heat-developable color photosensitive material of the present invention is not particularly limited, and various binders can be used, but hydrophilic binders are preferred. Alternatively, a hydrophobic binder can be optionally used depending on the purpose. For example, gelatin, gelatin derivatives, casein, sodium caseinate,
Proteins such as albumin, cellulose derivatives such as ethylcellulose, polysaccharites such as dextran, polysaccharides such as agar, gum arabic,
These include natural substances such as gum tragacanth, synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyvinyl acetal, as well as latex-like vinyl compounds and synthetic polymers that increase the dimensional stability of photographic materials. It's okay. Suitable synthetic polymers include U.S. Pat.
Examples include those described in the specifications of No. 3220844, No. 3287289, and No. 3411911. Useful polymers include water-insoluble polymers based on alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates. Suitable polymeric substances include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride,
Chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate phthalate can be mentioned. If necessary, two or more types may be used in combination. In addition to the above-mentioned components, various additives may be added to the heat-developable color photosensitive material of the present invention, if necessary. For example, as a development accelerator, US Pat.
Alkali release agents described in the specifications of No. 3220846, No. 3531285, No. 4012260, No. 4060420, No. 4088496, No. 4207392, or RD15733, No. 15734, No. 15776, etc.; −12700, −CO as described in U.S. Pat. No. 3,667,959
-, -SO ₂ -, -SO- group-containing non-aqueous polar solvent compounds, and as color tone adjusting agents, for example,
No. 46-4928, No. 46-6077, No. 49-5019, No. 49
-5020, 49-91215, 49-107727, 49-107727, 49-91215, 49-107727,
No. 50-2524, No. 50-67132, No. 50-67641, No. 50-67641, No. 50-67132, No. 50-67641, No.
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. 54-156525, No. 54-156526, No. 55-
Publications such as No. 4060, No. 55-4061, No. 55-32015, and West German Patent Nos. 2140406 and 2147063
No. 2220618, U.S. Patent No. 3080254, U.S. Pat.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzene, which are compounds described in the specifications of No. 3847612, No. 3782641, No. 3994732, No. 4123282, No. 4201582, etc. Oxazine, naphthoxazinedione, 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., 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. Also, patent application No. 57-73215, No. 57-
3-amino-5- described in 76838
Mercapto-1,2,4-triazoles, 3-
Acylamino-5-mercapto-1,2,4-triazoles are also effective. In addition, as antifoggants, for example, Japanese Patent Publication No. 11113/1982, Japanese Patent Publication No. 90118/1973, Japanese Patent Publication No. 49-90118,
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (for example, N-halogen Acetamide, N-
halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.),
Or sulfur-containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthion, polysulfide compounds, etc.), others, oxazoline, 1,2,4-triazole, Examples include compounds such as phthalimide. In addition, as a stabilizer, a printout preventive agent that particularly prevents printout after processing may be used at the same time, for example, JP-A No. 48-45228, No.
Halogenated hydrocarbons described in 119624, 50-120328, 53-46020, etc., specifically tetrabromobutane, tribromoethanol, 2-
Bromo-2-tolylacetamide, 2-bromo-
2-Tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4
-bis(tribromomethyl)-6-methyltriazine and the like. In the present invention, as the hardening agent for the hydrophilic binder, a usual gelatin hardening agent is preferably used, and for example, the following compounds are used. Inorganic salts such as chromium alum and chromium acetate; aldehydes such as formalin, glyoxal, and glutaraldehyde; N-methylols such as dimethylolurea and methylolsimethylhydantoin; 2,3-butanedione, 1,2-cyclopentanedione Ketones such as; carbamic acids such as dimethylcarbamoylpyridinium chloride; sulfonic acid esters such as trimethylene bis(methane sulfonate); sulfonyl halides such as ethylene bis(sulfonyl fluoride); bis(2-chloroethyl)urea, 2, 4-
Active halogens such as dichloro-6-hydroxy-s-triazine; Mucohalogen acids such as mucochloric acid, mucobromic acid, and mucophenoxychloric acid; Epoxies such as diglycidyl ether;
Aziridines such as triethylene melamine and hexamethylene bis(aziridinylcarboxamide);
1-ethyl-3-(3'-dimethylaminopropyl)
Carbodiimide hydrochloride; active olefins such as 1,3-bis(acryloyl)urea, divinyl ketone, diacrylamide, 1,3,5-triacryloylhexahydro-s-triazine bis(vinylsulfonyl)ether; polyvinyl alcohol and malein Polymer curing agents with functional groups such as partial acid esters and copolymers of glycidyl acrylate. Regarding the above curing agent, please refer to JP-A No. 51-78788,
No. 53-139689, No. 56-27135, U.S. Patent
No. 3843372, No. 1870354, No. 2080019, No. 3843372, No. 1870354, No. 2080019, No.
No. 2726162, No. 2870013, No. 2983611, No.
No. 2992109, No. 3047394, No. 3057723, No.
No. 3103437, No. 3321313, No. 3325287, No. 3325287, No. 3321313, No. 3325287, No.
No. 3362827, No. 3543292, British Patent No. 676628, No. 3543292, British Patent No. 676628,
No. 825544, No. 1270578, German Patent No. 672153,
It is described in Japanese Patent Publication No. 1090427, Japanese Patent Publication No. 34-7133, Japanese Patent Publication No. 46-1872, and Research Disclosure, Vol. 176, p. 26 (December 1978). Particularly preferred curing agents include U.S. Pat.
No. 3868257, No. 4088495, No. 4134765, No.
No. 4137082, No. 4161407, JP-A-49-116154,
No. 49-118746, No. 53-57257, No. 53-666960
No. 58-50535, Special Publication No. 47-24259, No. 49-
13563 etc., at least 2 in the molecule
Compounds having six or more vinylsulfonyl groups can be mentioned. This compound, for example,
It can be advantageously used by dispersing it in a hydrophilic colloid, as in the method described in No. 55-142330. 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;
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 include a spectral sensitizer, an antihalation dye, a fluorescent sensitizer, a hardener, an antistatic agent, a plasticizer, a spreading agent, Various additives, coating aids, etc. may be added. The heat-developable photosensitive layer of the heat-developable color photosensitive material of the present invention basically consists of three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and each absorbs blue, green, and red light, which are the three primary colors of light. Absorb. These three layers release or form dyes corresponding to the three primary colors of yellow, magenta and cyan, respectively, by thermal development. Basically, the blue-sensitive layer forms or releases yellow dye, the green-sensitive layer forms or releases magenta dye, and the red-sensitive layer forms or releases cyan dye, but the combination is not necessarily limited to this. Further, the heat-developable photosensitive layer may be divided into two or more layers (for example, a high-sensitivity layer and a low-sensitivity layer). In addition to the photosensitive layer, the heat-developable color photosensitive material of the present invention can be provided with various photographic constituent layers such as an overcoat layer, an undercoat layer (undercoat layer), a backing layer, an intermediate layer, or a filter layer depending on the purpose. . The photosensitive layers and other photographic constituent layers of this invention can be coated on a wide variety of supports. Supports used in the present invention include plastic films such as cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyamide film, polyethylene film, polyethylene terephthalate film, and polycarbonate film, metals such as aluminum, glass, and even paper. , baryta paper, synthetic paper, etc. can also be used. Also, among these supports, those with a small thermal expansion/contraction rate are preferred. The light-sensitive material of the present invention forms a color image on an image-receiving element by imagewise exposure, development by heat treatment, and thermal transfer to an image-receiving element in a stacked relationship with the light-sensitive material. The above-mentioned image receiving element basically only needs to have the function of stopping the transfer of the imagewise distribution of the thermally transferred dye and fixing it. For example, it may simply be a layer of gelatin or other synthetic polymer, or it may be a layer of wood pulp or other synthetic pulp fibers. Also, various mordants may be used. The image-receiving element may also include the image-receiving element on a suitable support, and the support may also serve as the image-receiving element. Further, the image-receiving layer (element) may be formed on the same support as the support of the light-sensitive material of the present invention. Further, after the dye image is transferred to the image-receiving element, the image-receiving element may be peeled off, or it may be integrated with the photosensitive layer. Additionally, an optional opacifying layer (reflective layer) can be included, which layer reflects the desired degree of radiation, such as visible light, that can be used to observe the dye image in the receiver element. is used for. The opacifying layer can contain various agents that provide the necessary reflection, such as titanium dioxide. Effective image-receiving elements (which may have a separate support or serve as a support) include synthetic polymer films such as polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, Examples include ethyl cellulose film and other papers such as baryta paper, art paper, ivory paper, and plain paper. Particularly preferred image receiving elements have a synthetic polymer layer on a support, such as a baryta support with a polyvinyl chloride layer or a polycarbonate layer, a polyethylene terephthalate film support with a polyvinyl chloride layer, or a polyvinyl chloride layer on a polyethylene terephthalate film support. Some have a polycarbonate layer or a polycarbonate layer. These are described in Japanese Patent Application Nos. 58-97907 and 58-128600. Furthermore, polyvinyl chloride containing polyalkylene carbonate disclosed in JP-A-53-246;
Polyvinyl chloride containing silicone oil, as disclosed in Nos. 51-88543 and 52-40557, and polyvinyl chloride with plasticizer retained by plasma treatment are also useful as image-receiving layers. Various exposure means can be used for the color diffusion transfer type heat-developable color photosensitive material of the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Light sources commonly used for regular color printing, such as tungsten lamps, mercury lamps,
A xenon lamp, laser beam, CRT or LED beam, etc. can be used as the light source. The original drawing may be a line image such as a technical drawing or a photographic image with gradation. Furthermore, the printing from the original drawing may be done by contact printing. In addition, images projected by video cameras, etc., and image information sent from television stations can be directly transmitted to CRT or
It is also possible to send the image to OFT and form the image on a heat-developable photosensitive element using a contact lens or a lens and then print it. Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means and display means in various devices. this
It is difficult to create an LED that effectively emits blue light. In this case, to play a color image,
It is sufficient to use LEDs that emit green, red, and infrared light, and to design layers that are sensitive to these lights to provide yellow, magenta, and cyan pigments, respectively. That is, the green light-sensitive layer may contain a yellow dye-providing compound, the red light-sensitive layer may contain a magenta dye-providing compound, and the infrared light-sensitive layer may contain a cyan dye-providing compound. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
It is read by a light-receiving element such as a CCD, is stored in a memory of a computer, etc., and this information is processed as necessary through so-called image processing, and then this image information is reproduced on a CRT and used as an image-like light source. A method of directly causing three types of LEDs to emit light based on the processed information can also be applied. Image receiving layer (element) for thermal transfer from the photosensitive material of the present invention
Thermal transfer is carried out when the photosensitive material of the present invention is thermally developed or when it is reheated after thermal development. For heating for thermal transfer, all methods applicable to ordinary heat-developable photosensitive materials can be used. For example, it may be brought into contact with a heated block or plate, brought into contact with a heated roller or drum, passed through a high-temperature atmosphere, or using high-frequency heating, and furthermore, in the photosensitive material of the present invention or for thermal transfer. By providing a conductive layer in the image receiving layer (element), it is possible to utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including preheating and then reheating, a short period of time at a high temperature, a long period of time at a low temperature, continuous rise, fall, or repetition, and even discontinuous heating. Although heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. Usually, the heating temperature during transfer is 80℃ ~
The temperature is 200°C, preferably 100°C to 180°C, and the heating time is usually 1 second to 5 minutes, preferably 5 seconds to 3 minutes. For thermal transfer using the photosensitive material of the present invention, a commercially available thermal developing machine can be easily used. for example,
“Image Forming Model 4634” (Sony Tektronix), “Deiberotsu Parmodule 277”
(3M Company), “Video Hard Copy Unit NWZ-
301'' (Japan Radio Co., Ltd.) etc. [Examples] Examples of the present invention are shown below, but the embodiments of the present invention are not limited to these. Example 1 The following A coating solution for heat-developable color photosensitive materials containing the components (a) to (g) was prepared. (a) Average particle size of photosensitive silver halide formed in photographic gelatin
0.125μm silver iodobromide (AgBr:AgI=97:3) sensitized with sulfur and made green sensitive with cyanine dye, equivalent to 0.2g of silver. (b) Organic silver salt in poly(N-vinylpyrrolidone) aqueous solution,
4-sulfobenzotriazole and silver nitrate were reacted in equimolar amounts, equivalent to 0.2 g of silver. (c) Developer 0.35g of the following developer synthesized by the method shown in JP-A-56-146133. (d) Dye-providing compound 0.54 g of the following compound was dissolved in dioctyl phthalate and ethyl acetate, mixed with an aqueous gelatin solution containing dodecylbenzenesulfonic acid, and made into an oil-in-water dispersion using a homogenizer. (e) Binder Including those contained in each of the above components, 0.64 g of gelatin and 1.44 g of poly(N-vinylpyrrolidone). (f) Development accelerator (g) Heat solvent 1.6 g of 1,6-hexanediol However, the compounds shown in Table 1 were added as an oil-in-water dispersion together with the dye-providing compound, and the pH of each coating solution was adjusted to 5.5. It was coated on photographic polyethylene terephthalate film that had been subbed.

[Table] The obtained samples No. 1 to No. 2 were exposed to 1600 CMS through a Wrathten filter No. 99 (manufactured by Eastman Kodak Co., Ltd.) and a step wedge. On the other hand, polyvinyl chloride-containing latex NIPOL G-576 (manufactured by Nippon Zeon Co., Ltd.) was coated on photographic baryta paper and passed through an atmosphere at 150°C to form a smooth film, which was used as an image receiving element for thermal transfer. The heat-developable color light-sensitive material of the above exposure agent and the image-receiving element for thermal transfer are superimposed and heat-developed at 140°C for 1 minute using Deiberotsu Parmodule 277 (manufactured by 3M) to immediately transform the image-receiving element. I tore it off. Table 2 shows the minimum density (Dmin) and maximum density (Dmax) of the obtained cyan transfer image.

[Table] The above dye-providing compound was changed to the following,
Compound AF-24 of the present invention and L-ascorbyl palmitate other than the present invention were each 1.2×10 ^-4 mol
When L-ascorbyl palmitate was added and the same operation as Samples 1 and 2 was performed, the fog increased compared to the one without L-ascorbyl palmitate, whereas the compounds of the present invention all lowered the maximum concentration. It showed anti-fogging effect without any problems. [Effects of the Invention] According to the present invention, a color diffusion transfer type heat-developable photosensitive material can provide a dye image with a high maximum density and little fog.

Claims (1)

[Scope of Claims] 1. On a support, at least (a) photosensitive silver halide, (b) organic silver salt, (c) developer, (d) dye-providing compound,
(e) A heat-developable color photosensitive material having at least one heat-developable photosensitive layer containing a binder,
At least one layer of the heat-developable photosensitive layer has the following general formula (1):
A heat-developable color photosensitive material containing a compound represented by: General formula (1) [In the formula, R ₆ , R ₇ and R ₈ are each hydrogen atom, halogen atom, alkyl group, aryl group, acyl group, alkyloxycarbonyl group, aryloxycarbony group, alkylsulfonyl group, arylsulfonyl group, alkylamino group, arylamino group, carbamoyl group, acylamino group, alkoxy group, sulfamoyl group, sulfonylamino group, sulfo group, carboxy group or hydroxy group. R ₅ and R ₉ represent an alkyl group. However, the total number of carbon atoms in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is 8
That's all.