JPH0146056B2 - - 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, such as JP-A-57-179840;
No. 186744, No. 57-198458, No. 57-207250, 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, which causes unpredictable thermal fog.
The mechanism for this is thought to be the occurrence of fog on the surface of the 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 U.S. Pat. No. 3,589,903,
N-halogen compounds of West German Patent No. 2402161, peroxides of West German Patent No. 2500508, sulfur compounds of West German Patent No. 2617907, palladium compounds of US Patent No. 4102312, sulfinic acids of Japanese Patent Publication No. 53-28417, Research Disk Examples include Rosier No. 169077, mercaptotriazole of Rosier No. 169079, and 1,2,4-triazole of US Pat. No. 4,137,079. However, these thermal fog inhibitors 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, and so no effective antifoggants have 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 invention is that high maximum concentrations are obtained;
Another object of the present invention is to provide a heat-developable color photosensitive material that causes less fog. [Structure of the Invention] The object of the present invention is to form on a support at least one heat-developable photosensitive layer containing at least (a) a photosensitive silver halide, (b) an organic silver salt, (c) a developer, (d) a dye-providing compound, and (e) a binder. In the heat-developable color photosensitive material, at least one layer of the heat-developable photosensitive layer contains a compound represented by the following general formula (1) or (2) and a benzotriazole represented by the following general formula (3) or a derivative thereof. This was achieved by using a heat-developable color photosensitive material. In the above formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ and R ₈
are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably a 1-24 alkyl group, such as methyl, ethyl, butyl, t-amyl, t-octyl, Groups such as n-dodecyl, n-pentadecyl, and cyclohexyl can be mentioned, but further aryl groups, such as benzyl groups and phenethyl groups as alkyl groups substituted with phenyl groups), substituted or unsubstituted Aryl groups (e.g. phenyl, naphthyl, tolyl, mesityl), acyl groups (e.g. acetyl, tetradecanoyl, bivaloyl, substituted or unsubstituted benzoyl), alkyloxycarbonyl groups (e.g. methoxycarbonyl) , 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) alkylamino group (e.g. ethylamino group, t-octylamino group), arylamino group (e.g. anilino group, further substituted with a substituent such as a halogen atom, an alkyl group, an amide group or an imido group) anilino group), carbamoyl group (e.g. substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-
Methyl-N-dodecylcarbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, specifically 2,4-di-t-phenoxybutyl, carbamoyl group, substituted or unsubstituted phenylcarbamoyl group, specifically is a 2-dodecyloxyphenylcarbamoyl group, etc.), a substituted or unsubstituted acylamino group (e.g., n-butylamide group,
laurylamide group, optionally substituted β-phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamideethylamide group, β-methoxyethylamide group), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, an octadecyloxy group, etc.), a sulfamoyl group (such as a methylsulfamoyl group, an n-dodecylsulfamoyl group, a substituted or unsubstituted phenyl group), (e.g., dodecylphenylsulfamoyl group, etc.), an alkylsulfonylamino group or an arylsulfonylamino group (e.g., a methylsulfonylamino group, a tolylsulfonylamino group), or a sulfo group, a carboxy group, or a hydroxyl group. etc. 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 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 ₁ , R ₂ , R ₃ and R ₄ is 8 or more, and the total number of carbon atoms in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is 8 or more. In the above formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group, an acyl group, an alkyloxycarbamoyl group, an aryloxycarbonyl group. , alkylsulfonyl group, arylsulfonyl group, alkylamino group, arylamino group, carbamoyl group, acylamino group, alkoxy group,
Represents a sulfamoyl group, alkylsulfonylamino group, nitro group, amino group, hydroxy group, carboxy group or sulfo group. Specific examples of the compound represented by the general formula (1) or (2) 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 performed using METHODEN
DER ORGANISCHEN CHEMIE (HOUBEN−
WEYL) BAND V1/1C PHENOLE Teil 1
(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 1 mol of silver contained in the heat-developable photosensitive layer.
0.5 mol, preferably in the range of 0.005 to 0.2 mol. The method of adding the compound of the present invention is not particularly limited, but
Preferably used are a method in which the compound is added after being dissolved in a high boiling point solvent, and a method in which a compound having a hydrophilic group is added after being dissolved in an alkaline solution is preferably used. 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 ₁ , R ₂ , R ₃ and R ₄ 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. Further, the compound of the present invention can also be used in combination with a quinone compound as shown in JP-A-55-161238. In the present invention, benzotriazole or a derivative thereof (hereinafter, both thereof will be referred to as a benzotriazole derivative) is represented by the following general formula (3). In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom, an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group,
ethyl group, t-butyl group, t-octyl group), substituted alkyl group (e.g. trichloromethyl group, methylol group, β-hydroxyethyl group, β-methoxyethyl group), aryl group (e.g. phenyl group,
tolyl group), acyl group (e.g. acetyl group, pivaloyl group, benzoyl group), alkyloxycarbonyl group (e.g. methoxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), alkylsulfonyl group (e.g. methylsulfonyl group) ), arylsulfonyl group (e.g. phenylsulfonyl group), alkylamino group (e.g. ethylamino group), arylamino group (e.g. anilino group), carbamoyl group (e.g. methylcarbamoyl group), acylamino group (e.g. acetamido group, benzamide group) ), alkoxy groups (e.g. methoxy group), sulfamoyl groups (e.g. methylsulfamoyl group), alkylsulfonylamino groups (e.g. methylsulfonylamino group),
Represents a nitro group, amino group, hydroxy group, carboxy group or sulfo group. These benzotriazole derivatives are used in an amount of 0.001 mol to 10 mol, per 1 mol of organic silver salt in the same layer.
Preferably it is added in an amount of 0.01 mol to 2 mol. Moreover, two or more types of benzotriazole derivatives may be used in combination. In the present invention, the benzotriazole derivative preferably has a hydrophilic group. In the present invention, the hydrophilic group is a hydroxy group,
Indicates an amino group, a carboxy group, a sulfo group, a carbamoyl group, a sulfamoyl group, and an acylamino group. Specific examples of benzotriazole derivatives having a hydrophilic group that are preferably used in the present invention are shown below. BT-(1) 4-hydroxybenzotriazole BT-(2) 5-hydroxybenzotriazole BT-(3) 4-sulfobenzotriazole BT-(4) 5-sulfobenzotriazole BT-(5) 4-carboxybenzotriazole BT-(6) 5-carboxybenzotriazole BT-(7) 5-carbamoylbenzotriazole BT-(8) 4-sulfamoylbenzotriazole BT-(9) 5-carboxy-6-hydroxybenzotriazole BT-(10 ) 5-Carboxy-7-sulfobenzotriazole BT-(11) 4-hydroxy-5-sulfobenzotriazole BT-(12) 4-hydroxy-7-sulfobenzotriazole BT-(13) 5,6-dicarboxybenzo Triazole BT-(14) 4,6-dihydroxybenzotriazole BT-(15) 4-hydroxy-5-chlorobenzotriazole BT-(16) 4-hydroxy-5-methylbenzotriazole BT-(17) 4-hydroxy- 5-methoxybenzotriazole BT-(18) 4-hydroxy-5-nitrobenzotriazole BT-(19) 4-hydroxy-5-cyanobenzotriazole BT-(20) 4-hydroxy-5-aminobenzotriazole BT-( 21) 4-hydroxy-5-acetamidobenzotriazole BT-(22) 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole BT-(23) 4-hydroxy-5-carboxymethylbenzotriazole BT-(24) 4-hydroxy -5-phenylbenzotriazole BT-(25) 4-sulfo-5-chlorobenzotriazole BT-(26) 4-sulfo-5-methylbenzotriazole BT-(27) 4-sulfo-5-methoxybenzotriazole BT -(28) 4-Sulfo-5-cyanobenzotriazole BT-(29) 4-sulfo-5-aminobenzotriazole BT-(30) 4-sulfo-5-acetamidobenzotriazole BT-(31) 4-hydroxy- 5-Carboxybenzotriazole BT-(32) 4-sulfo-5-phenylbenzotriazole BT-(33) 4-sulfo-5-methoxy-6-chlorobenzotriazole BT-(34) 4-sulfo-5-chlor -6-carboxybenzotriazole BT-(35) 4-carboxy-5-chlorobenzotriazole BT-(36) 4-carboxy-5-methylbenzotriazole BT-(37) 4-carboxy-5-nitrobenzotriazole BT- (38) 4-carboxy-5-aminobenzotriazole BT-(39) 4-carboxy-5-methoxybenzotriazole BT-(40) 4-carboxy-5-acetamidobenzotriazole BT-(41) 4-carboxy-5 -Phenylbenzotriazole BT-(42) 4-carboxy-5-methyl-7-
Sulfobenzotriazole BT-(43) 4,6-disulfobenzotriazole BT-(44) 4-sulfo-6-chlorobenzotriazole BT-(45) 5-acetamidobenzotriazole Conventionally, general formula (1) or (2) The antifogging effect of the compound shown in ) was not necessarily sufficient under conditions where a high maximum concentration was maintained. on the other hand,
Regarding the antifogging effect by adding the benzotriazole compound represented by the general formula (3), the effect of reducing high fog was remarkable, but it did not reach the ideal level as desired by the present inventors. The present invention provides a compound represented by the general formula (1) or (2) and a benzotriazole compound represented by the general formula (3), which are superior in their anti-fogging effects by far exceeding their respective antifogging effects, and are superior to those of a mere combination. It was something that could not have been predicted. 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 in the range of 0.001 to 100 mol, preferably 0.05 to 10 mol, per 1 mol of organic silver salt. 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 particles. 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 No. 49-52626, 52-
No. 31728, No. 52-13731, No. 52-141222, No. 53
-36224, 53-37610, U.S. Patent No.
Silver salts of aliphatic carboxylic acids described in specifications such as No. 3330633 and No. 4168980, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc. Also, silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., silver salts having an imino group, such as silver benzotriazole, silver saccharin, silver phthalazinoic acid, silver phthalimide, etc., and silver compounds having a mercapto group or a thione group. salts such as silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver mercaptobenzothiazole, 2
- silver mercaptobenzimidazole, silver 3-mercaptophenyl-1,2,4-triazole, or otherwise 4-hydroxy-6-methyl-
Examples include silver 1,3,3a,7-tetrazaindene and silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene. Further, silver compounds such as those described in Research Disclosure (RD) Nos. 16966 and 16907, and British Patent Nos. 1590956 and 1590957 can also be used. Among these, silver salts having an imino group such as benzotriazole silver salts are preferred, and examples of benzotriazole silver salts include benzotriazole silver,
Alkyl-substituted benzotriazole silver such as methylbenzotriazole silver, halogen-slowed benzotriazole silver such as prombenzotriazole silver, chlorobenzotriazole silver, amide-substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and Compounds described in British Patent No. 1590956 and British Patent No. 1590957, for example, N-[6-chloro-4-N(3,5-
dichloro-4-hydroxyphenyl)imino-1
-oxo-5-methyl-2,5-cyclohexadien-2-yl]-5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1
-benzotriazol-5-ylazo-2-naphthol silver salt, N-benzotriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt, and the like. Particularly useful organic silver salts in the present invention are
It has a hydrophilic group as shown in No. 58-118638. 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.
0.05g to 10.0g, preferably 0.2g to 5.0g
It is. 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 and sulfonamide phenol type developing agents, and hydrazone type color developing agents described in JP-A No. 57-186744, etc. Special request 1987-
No. 122596, No. 57-160698, No. 57-126054, No.
Thermal transferable dye-providing compounds described in Nos. 58-33363 and 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, U.S. Patent No.
No. 3342599, No. 3719492, JP-A-53-135628
Color developing agent precursors described in No. 54-79035 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. 1798-229648
No. 57-229672, No. 57-225928, etc.
These do not necessarily need to use the above-mentioned developer, and the following developers can be used. That is, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-t
-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol,
2,6-dichloro-4-benzenesulfonamide phenol, 2,6-dibromo-4-(p-toluenesulfonamide) phenol, etc.], or polyhydroxybenzenes (e.g. hydroquinone, t-butylhydroquinone, 2,6-dibromo-4-(p-toluenesulfonamide) phenol, etc.) -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'-bunaphthyl, 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)-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-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 type of other additives, but it is usually in the range of 0.05 mol to 10 mol per mol of organic silver salt. and preferably 0.1 mol to 3 mol. 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. 58-123533, 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 is represented by the following general formula (1).
It can be expressed as General formula () Cp-X In the formula, Cp represents a coupler residue excluding the hydrogen atom at the active position, and Cp represents a sulfo group,
A coupler residue that does not have a hydrophilic group such as a carboxy group and a group containing such a hydrophilic 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 sulfo groups or carboxy groups, or groups 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). , such as methyl, ethyl, butyl, t-octyl, n-dodecyl, n-
Examples include groups such as pentadecyl and cyclohexyl, and examples of alkyl groups substituted with aryl groups, such as phenyl groups, include benzyl groups,
phenethyl group), substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group), acyl group (e.g. acetyl group, tetradecanoyl group, bivaloyl group, substituted or unsubstituted aryl group) benzoyl group), alkyloxycarbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group), alkyl Sulfonyl group (e.g. methylsulfonyl group), arylsulfonyl group (e.g. phenylsulfonyl group), carbamoyl group (e.g. substituted or unsubstituted alkylcarbamoyl group, methylcarbamoyl group, butylcarbamoyl group, chitradecylcarbamoyl group,
N,-methyl-N-dodecylcarbamoyl group, optionally substituted phenoxyalkylcarbamoyl group, specifically, 2,4-di-t-phenoxybutyl-carbamoyl group, substituted or unsubstituted phenylcarbamoyl group 2-dodecyloxyphenylcarbamoyl group, etc.), substituted or unsubstituted acylamino groups (e.g., n-butylamide group, laurylamide group, optionally substituted β-phenoxyethylamide group, enoxyacetamide 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. Furthermore, R ₅ is an alkyl group (preferably a carbon number of 1
~24 alkyl groups, such as methyl, butyl,
heptadecyl group), an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group,
ethoxy group, octadecyloxy group), arylamino group (e.g. anilino group, or anilino group substituted with a substituent such as a halogen atom, alkyl group, amide group or imide group), substituted or unsubstituted alkylamide group ( For example, laurylamide, optionally substituted phenoxyacetamide, phenoxybutanamide groups), substituted or unsubstituted arylamide groups (such as benzamide groups, and halogen atoms, alkyl groups, alkoxy groups, amide groups, etc.). (substituted benzamide group), etc. 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.). In addition, R ₁₁ , R ₁₂ .R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are
It represents a group having the same meaning as the group represented by R ₁ and R ₂ above. Typical specific examples of the dye-providing compound represented by general formula (1) include the following compounds. [Exemplary dye-providing compound] In addition, polymeric dye-donating compounds such as the following dye-donating substances (13), (14), and (15), which are obtained by adding a polymerizable group to the molecule and polymerizing them alone or with other copolymerization components, can be used. It can also be used. The dye-providing compound used in the present invention varies depending on the photothermographic composition, coating conditions, processing method, etc., but is approximately 0.01 mol to 1 mol of organic silver salt.
Used in a range of 10 mol, preferably 0.1 mol to
It is 2.0 mol. 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 dispersion method as described above, 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-providing compounds dissolved in the solvent may be used in combination with anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants 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, and preferably in a range of 0.05 to 100 parts per part of the dye-providing compound. A preferable dispersion method other than the above is Fischer dispersion. Fischer dispersion refers to dissolving and dispersing a dye-providing compound 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 that is compatible with water can be used, and after dissolving and dispersing the dye-providing compound,
PH can be adjusted. In this case, an organic or inorganic acid compatible with water can be used as the PH adjuster. Surfactants as dispersion aids are
Anionic or nonionic activators may be used, but anionic activators are preferred. Note that the above-mentioned Fisher dispersion is sometimes called Agfa dispersion, and the technical contents described in British Patent No. 45555, British Patent No. 465823, British Patent No. 29897, etc. can be referred to. (e) Binder 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, with a hydrophilic binder being 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 mixed solution of water and an organic solvent (a solvent that is optionally miscible with water). For example, proteins such as gelatin, gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, and useful polymers include polyvinyl acetals (preferably with a degree of acetalization below 20%, e.g. polyvinyl butyral), Preferred are polyacrylamide, polyvinylpyrrolidone, ethyl cellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), but are not limited to these. Moreover, if necessary, two or more kinds 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 1/10 to 10 parts, preferably 1/4 to 4 parts by weight, 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, proteins such as casein, sodium caseinate, albumin, cellulose derivatives such as ethylcellulose, polysaccharites such as dextran, polysaccharides such as agar, natural substances such as gum arabic, gum tragacanth, etc., polyvinyl alcohol, polyvinylpyrrolidone, or Synthetic polymers such as water-soluble polyvinacetals may also be included, as well as latex-like vinyl compounds and synthetic polymers such as those described below that increase the dimensional stability of the photographic material. Suitable synthetic polymers include U.S. Pat.
Examples include those described in the specifications of No. 3062674, 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, polyvinyl pyrrolidone, polystyrene, ethyl cellulose,
Polyvinyl chloride, chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polypinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propio nate, cellulose acetate phthalate. 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.; −Organic acids described in US Pat. No. 12700, − as described in US Pat. No. 3,667,959
Non-aqueous polar solvent compounds having COO-, _-SO2- , -SO- groups, and color tone adjusting agents include, for example, JP-A No. 46-4928, JP-A No. 46-6077, JP-A No. 49-5019;
No. 49-5020, No. 49-91215, No. 49-107727,
No. 50-2524, 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-
No. 156524, No. 54-156525, No. 54-156526, No. 54-156525, No. 54-156526, No.
Publications such as No. 55-4060, No. 55-4061, and No. 55-32015, as well as West German Patent No. 2140406 and No.
No. 2147063, No. 2220618, U.S. Patent No. 3080254
No. 3847612, No. 3782941, No. 3782941, No. 3847612, No. 3782941, No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, 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 mergatotriazole, dimercaptotetrazapentalene,
There are phthalic acid, naphthalic acid, phthalamic acid, etc., and mixtures of one or more of these with imidazole compounds, or mixtures of at least one acid or acid anhydride such as phthalic acid, naphthalic acid, etc. and phthalazine compounds, and Examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also special request 1987
-73215, 3 described in the specification of No. 57-76838
-Amino-5-mercapto-1,2,4-triazoles, 3-acylamino-5-mercapto-
1,2,4-triazoles are also effective. In addition, as an antifoggant, for example, Japanese Patent Publication No. 11113/1982, Japanese Patent Publication No. 90118/1973, Japanese Patent Publication No. 49-90118,
No. 10724, No. 49-97613, No. 50-101019, No. 49
-130720, 50-123331, 51-47419,
No. 51-57435, No. 51-78227, No. 51-104338
No. 53-19825, No. 53-20923, No. 51-
No. 50725, No. 51-3223, No. 51-42529, No. 51-
Publications such as No. 81124, No. 54-51821, and No. 55-93149, as well as British Patent No. 1455271 and US Patent No.
3885968, 3700457, 4137079, 4138265, and West German Patent No. 2617907, or oxidizing agents (such as N-halogenoacetamide). , N
-halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), or acids and their salts (such as sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), or sulfur Containing compounds (for example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthione, polysulfide compounds), other compounds such as oxazoline, 1,2,4-triazole, phthalimide, etc. Can be mentioned. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially for preventing printouts after processing.
Halogenated hydrocarbons described in 119624, 50-120328, 53-46020, etc., specifically tetrabromobutane, tribromoethanol, 2-
Promo-2-tolylacetamide, 2-bromo-
2-Tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4
-bis(tribromomethyl)-6-methyltriazine and the like. In the present invention, as a hardening agent for the hydrophilic binder, a usual gelatin hardening agent is preferably used, and for example, a compound of chemical compound is used. Inorganic salts such as chromium alum and chromium acetate; aldehydes such as formalin, glyoxal, and glutaraldehyde; N-methylols such as dimethylol urea and methylol dimethylhydantoin; 2,3-butanedione, 1,2-cyclopentanedione, etc. Ketones; Carbamic acids such as dimethylcarbamoylpyridinium chloride; Sulfonic acid esters such as trimethylene bis(methanesulfonate); 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 glycidyl acrylate copolymers. Regarding the above curing agent, please refer to JP-A No. 51-78788,
No. 53-139689, No. 56-27135, U.S. Patent No.
No. 3843372, No. 1870354, No. 2080019, No. 2726162, No. 2870013, No. 2983611,
Same No. 2992109, Same No. 3047394, Same No. 3057723,
Same No. 3103437, Same No. 3321313, Same No. 3325287,
No. 3362827, No. 3543292, British Patent No.
German Patent No. 676628, German Patent No. 825544, German Patent No. 1270578, German Patent No. 672153, German Patent No. 1090427, Special Publication No. 1973-
It is described in No. 7133, 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. 4137082, No. 4161407, JP-A-49-116154
No. 49-118746, No. 53-57257, No. 53-
No. 666960, No. 58-50535, Special Publication No. 47-24259,
Examples include compounds having at least two or more vinylsulfonyl groups in the molecule, as described in No. 49-13563. This compound can be advantageously used by dispersing it in a hydrophilic colloid, for example, as described in JP-A-55-142330. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium-based stabilizer breaker described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain an activator stabilizer precursor, etc., 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 sensitizing agent, an antihalation dye, a fluorescent sensitizer, a hardening agent, an antistatic agent, a plasticizer, a spreading agent, etc. Various additives, coating aids, etc. 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 emits 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 cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyamide film,
Plastic films such as polyethylene film, polyethylene terephthalate film, and polycarbonate film, metals such as aluminum, glass, and even paper, baryta paper, synthetic paper, etc. can be used. Moreover, among these supports, those having a small thermal expansion/contraction rate are preferable. 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. Further, the image receiving element may 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 integral with the photosensitive layer. Additionally, an optional opacifying layer (reflective layer) may be included, such layer reflecting the desired degree of radiation, such as visible light, that can be used to observe the dye image in the receiving element. It is used to make 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 may also serve as a support) include synthetic polymer films such as polyethylene terephthalate films, polycarbonate films,
Paper such as polyvinyl chloride film, polyvinylidene chloride film, ethyl cellulose film,
Examples include 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 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. In general, a light source used for normal color printing, such as a tungsten lamp, mercury lamp, xenon lamp, laser beam, CRT or LED beam, can be used as the light source. The original drawing may be a line image such as a technical drawing or a photographic image with gradation. Furthermore, the printing from the original drawing may be done by contact printing. In addition, images projected by video cameras, etc., and image information sent from television stations can be directly transmitted to CRT or
It is also possible to send the image to OFT and form the image on a heat-developable photosensitive element using a contact lens or a lens and then print it. In addition, 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. Based on the processed information, a method of directly emitting light from three types of LEDs for exposure 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 that can be applied 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. It is also possible to provide a conductive layer in the image-receiving layer (element) and utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of preheating and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, continuously increasing, decreasing, or repeating, and even discontinuously. 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℃~200℃,
The temperature is 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, it is easy to use a commercially available heat developing machine.
), “Video Hard Copy Unit NWZ-301”
(Japan Radio Co.) etc. can be easily applied. [Example] Examples of the present invention are shown below, but the embodiments of the present invention are not limited thereto. Example 1 The following components of a coating solution for heat-developable color photosensitive materials were prepared. (a) Photosensitive silver halide Average grain size 0.125μm Silver iodobromide (AgBr:Agl=93:
7) with the following sensitizing dye and 4-hydroxy-6
- Sulfur sensitization treatment with sodium thiosulfate in the presence of methyl-1,1,3a-7-tetrazaindene to give the following composition. Silver halide (in terms of silver) 381g Gelatin 190g/5000ml (b) Organic silver salt In a mixed solvent of 150ml of water and 150ml of ethanol, 45g of poly(N-vinylpyrrolidone), 20g of 4-sulfobenzotriazole, and water. sodium oxide
Dissolve 4.2g of 5N silver sulfate aqueous solution and stir.
ml, adjust the pH to 6-8, add water and make 400ml.
And so. (c) Developer An aqueous solution containing 27.3 g of poly(N-vinylpyrrolidone) and 6.2 g of photographic gelatin, a small amount of surfactant, 80 g of 1,6-hexanediol, 0.75 g of the following development accelerator, and 20 g of the following developer was added and dissolved to bring the pH to 7.0, and then water was added to make a total volume of 330 ml. (d) Dye-providing compound 53.8 g of the following dye-providing compound was dissolved in 54 g of dioctyl phthalate and 162 g of ethyl acetate, mixed with 1180 ml of a 3.6% gelatin aqueous solution containing 140 ml of a 5% aqueous solution of Alkanol XC (manufactured by DuPont), and mixed with a homogenizer. An oil-in-water dispersion was prepared. A coating liquid was prepared by mixing the above components as follows. (a) Photosensitive silver halide 14.2 ml (b) Organic silver salt 40 ml (c) Developer 3 ml (d) Dye-providing compound 70 ml (However, after mixing, keep at 35°C ± 1°C, adjust pH to 5.50, A small amount of the same hardening agent solution No. 4 of Example 1 was added in No. 142330/1983. compound of invention
One in which only AF-5 was added as an oil-in-water dispersion together with a dye-providing compound (Sample No. 2), one in which only compound BT-3 of the present invention was added as an aqueous solution (Sample No. 3), (Sample No. .2) Compounds of the invention
Added only BT-3 as an aqueous solution (sample
No. 3), the compound AF-5 of the present invention is added as an oil-in-water dispersion together with a dye-providing compound, and
Compound BT-3 of the present invention was added as an aqueous solution (sample No. 4), and AF-5 was added to AF in sample 4.
-7 (sample No. 5), and sample 4 with BT-3 replaced with BT-45 (sample No. 4).
6) was prepared, and a silver amount of 0.95
It was coated so that the amount was 2 g/m ² . The obtained samples No. 1 to No. 6 were exposed to 1600 CMS through a Wraten 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 then used as an image-receiving element for thermal transfer. The exposed heat-developable color light-sensitive material 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. Minimum density (Dmin) of the obtained cyan transfer image
and the maximum concentration (Dmax) are shown in Table-1.

[Table] As is clear from Table 1, Compound 2 of the present invention
By including seeds, Dmax is large and
Dmin is noticeably improved. Example 2 The same coating solution as in Example 1 was prepared except that 1,6-hexanediol in Example-1 was changed to petriol (3-methyl-1,3,5-pentanetriol, Clareisoprene Chemical Co.) However, one that does not contain the compound of the present invention (Sample No.
7), Compound AF-9 of the present invention added only as an aqueous solution (Sample No. 8), Compound BT of the present invention
-3 added as an aqueous solution (Sample No.
9) An aqueous solution containing the compounds AF-9 and BT-3 of the present invention (sample No. 10) was prepared. Coating, exposure and heat development were carried out in the same manner as in Example-1, and the minimum density (Dmin) of the obtained transferred image was
and the maximum density (Dmax) are shown in Table 2.

[Table] From Table 2, it can be seen that in the samples containing two types of compounds of the present invention, Dmin was significantly improved without decreasing Dmax. Example 3 The following three layers were sequentially coated on a photographic transparent polyethylene terephthalate film that had been subjected to an undercoating process. <First layer> Red-sensitive layer A layer containing the same components as in Example-1 except that the sensitizing dye in Example-1 was changed to the one below. <Second layer> Intermediate layer 2 parts gelatin, poly(N-vinylpyrrolidone)
A layer in which 8 parts of a mixed binder was applied at a concentration of 1.5 g/m ² and the following compound was contained therein. <Third layer> Green-sensitive layer A layer having the same components as in Example-1 except that the dye-providing compound in Example-1 was changed to the one below. For the first layer and third layer of the photothermographic material,
Samples that do not contain the compound of the present invention
No. 11), and a sample to which the compounds AF-7 and BT-3 of the present invention were added (sample No. 12) were applied. The obtained samples No. 11 and No. 12 were exposed to green light and red light through colored glass filters G-52 and R-68 (both manufactured by Toshiba) and a step wedge, and then dioctyl phthalate was applied on photographic baryta paper. Example-1
The same heat development was carried out. Table shows the minimum density (Dmin) and maximum density (Dmax) of the obtained transferred image.
Shown in 3.

〔Effect of the invention〕

By using the heat-developable color photosensitive material of the present invention, dye images with high maximum density and low fog can be obtained.

Claims (1)

[Scope of Claims] 1 At least one layer containing at least (a) photosensitive silver halide, (b) organic silver salt, (c) developer, (d) dye-providing compound, and (e) binder on a support. In a heat-developable color photosensitive material having a heat-developable photosensitive layer, at least one layer of the heat-developable photosensitive layer comprises a compound represented by the following general formula (1) or (2), and a benzotriazole represented by the following general formula (3). A heat-developable color photosensitive material characterized by containing a compound. [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group , alkylsulfonyl group, arylsulfonyl group, alkylamino group, arylamino group, carbamoyl group, acylamino group, alkoxy group, sulfamoyl group,
It represents an alkylsulfonylamino group, an arylsulfonylamino group, a sulfo group, a carboxy group, or a hydroxy group. R ₅ and R ₉ each represent an alkyl group. however
The total number of carbon atoms in R ₁ , R ₂ , R ₃ and R ₄ is 8 or more, and the total number of carbon atoms in R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is 8 or more. R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group, an acyl group, an alkyloxycarbamoyl group, an aryloxycarbonyl group, an alkylsulfonyl group , an arylsulfonyl group, an alkylamino group, an arylamino group, a carbamoyl group, an acylamino group, an alkoxy group, a sulfamoyl group, an alkylsulfonylamino group, a nitro group, an amino group, a hydroxy group, a carboxy group, or a sulfo group. ]