JPH0245179B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-developable color diffusion transfer photosensitive material, and more particularly to a heat-developable color diffusion transfer photosensitive material in which an image formed on a heat-developable photosensitive layer is diffusely transferred to a dye image-receiving layer to obtain a clear color image. . The conventionally known color photography method using photosensitive silver halide is superior to other color photography methods in terms of photosensitivity, gradation, image preservation, etc., and has been the most widely put into practical use. . However, in this method, wet processing is used for steps such as development, bleaching, fixing, and water washing, which takes time and effort, and there are concerns that the processing chemicals may cause pollution to the human body, or the processing room and There are many problems, such as concerns about contamination of workers by treatment chemicals, and furthermore, the labor and cost of waste liquid treatment. Therefore, there has been a demand for the development of a method for forming color images that allows dry processing. Black and white heat-developable photosensitive materials characterized by heat treatment in the development process have been known for a long time, and are described in, for example, Japanese Patent Publications No. 43-4921 and No. 43-4924. A photosensitive material comprising silver and a developer is disclosed. Furthermore, many color heat-developable photosensitive materials are also known, to which this black-and-white photothermographic material is applied. For example, US Patent No. 3531286, US Patent No. 3761270,
No. 3764328, (Research Disclosure, hereinafter
(abbreviated as RD) No. 15108, No. 15127, No.
U.S. Patent No. 3180731, RD No. 13443, U.S. Patent No. 14347, etc. contain leuco dyes, while U.S. Patent No. 3180731, RD No. 13443 and U.S. Pat. No. 14347, etc. contain leuco dyes. Regarding what was used, U.S. Patent No. 4235957, RD No. 14433,
No. 14448, No. 15227, No. 15776, No. 18137, and No. 19419, etc., include U.S. Patent No. 4124398, U.S. Pat.
No. 4,124,387 and No. 4,123,273 describe a method for thermally bleaching photothermographic materials. However, with these proposals regarding color heat-developable photosensitive materials, it is difficult or impossible to bleach or fix the black and white silver images formed at the same time, or even if it is possible, wet processing etc. are required. It is what you need. Therefore, these proposals make it difficult to obtain clear color images or require complicated post-processing. In addition, in order to avoid the above-mentioned difficulties, JP-A-57-179840, JP-A-57-186744, and JP-A-57-198458 disclose a silver image by releasing a diffusible dye by heat development and transferring it to an image-receiving layer. A heat-developable color photosensitive material is described in which a color image is obtained by separating a dye image. Also, in the patent application No. 122596-1987,
A method is described in which a sublimable dye is released by heat development and transferred to an image-receiving layer. Although these techniques have the advantage of being able to obtain color images with simple operations, they have the drawback of poor dye diffusion transferability or sublimation transferability. In addition, the reactivity during thermal development is poor, resulting in a small amount of dye produced, low image density, and high fogging density. On the other hand, there is a method in which a sublimable dye is sublimated and transferred in a binder to a specially provided image-receiving layer by heat development, and the dye is sublimated and transferred to the image-receiving layer (Japanese Patent Application No. 102487-1987, Japanese Patent Application No. 57-102487). No. 126054, 57-
No. 160698, etc.) have been proposed, which have solved most of the above-mentioned drawbacks, but are still insufficient. (Object of the Invention) Therefore, the first object of the present invention is to provide a color photosensitive material that can be dry processed. The second objective is to provide an improved color thermal transfer photosensitive material that can form color images through simple processing and also provides clear and high-quality color images.Furthermore, the third objective is to provide an improved color thermal transfer photosensitive material that has excellent reactivity in heat development. Another object of the present invention is to provide an improved color thermal transfer photosensitive material that can provide images with high maximum density and low minimum density, that is, low fog. (Structure of the Invention) The color thermal transfer photosensitive material that undergoes dry heat development, which is the object of the present invention, uses silver halide as a photosensitive material in a binder, and the organic silver salt that is the main component of the material to be developed (reduced) is The oxidation product of the developer produced by development is used as a medium for dye formation and diffusibility imparting from the dye-donating substance, and the reaction is caused by heat development, and the diffusible dye of the reaction product is transferred into the binder. Diffusion is used to form a dye image on the image-receiving layer, but compared to coupling in conventional wet color development of silver halide color light-sensitive materials, the coupling environment is extremely disadvantageous and the resulting dye image is extremely unsatisfactory. It was hot. The present inventors made efforts to eliminate the above-mentioned dissatisfaction, and as a result, in the series of development-coupling-diffusion steps in the thermal development process, by incorporating a thermal solvent into the photosensitive material, a significant coupling reaction was observed. discovered that it promotes However, on the one hand, it has the disadvantage of accompanied by an increase in minimum density, that is, fog. On the other hand, mercaptotriazoles represented by the above general formulas () to () are used as color toning agents in monochrome photosensitive materials subjected to heat development or wet development, and in some cases have a sensitizing or development accelerating effect. The derivative has a slight development accelerating effect in color photothermographic materials. However, when used in combination with the photosensitive material containing the above-mentioned thermal solvent, it exhibits a surprisingly excellent fog-inhibiting effect, contrary to the development acceleration, and does not impede the coupling reaction at all. Therefore, in the present invention, the desired high density and low fog can be realized as specific characteristics. That is, the characteristics of the present invention are the coupling promotion effect of a hot solvent,
It is composed of a fog suppressing effect based on the synergistic action of a heat solvent and a mercaptotriazole derivative, and an additive action that does not cancel out the two effects.To summarize, the present invention The purpose of
In a color thermal transfer light-sensitive material in which a dye image is formed on an image-receiving layer by heat development, a dye-providing substance and a heat solvent that provide at least a photosensitive silver halide, a diffusible dye, or a diffusible dye precursor on a support. and a color thermal transfer photosensitive material characterized by containing a compound represented by the following general formula (), (), () or (). General formula () General formula () General formula () General formula () (Mercaptotriazole derivative used in the present invention) Here, the general formula () In the formula, R ¹ represents a hydrogen atom, an amino group, or an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent, and R ² represents a hydrogen atom, an amino group, an alkyl group, an alkenyl group, or an aryl group. represents a group. In the general formula (), the alkyl group represented by R ¹ is a linear, branched or cyclic alkyl group preferably having 1 to 12 carbon atoms, and these alkyl groups may be substituted (substituted Examples of the group include hydroxy group, phenyl group which may be substituted with a halogen atom), such as methyl, dichloromethyl, trifluoromethyl, ethyl, propyl, 3-hydroxypropyl, butyl, isobutyl, tertbutyl,
Bentyl, isobentyl, hexyl, heptyl,
These groups include octyl, decyl, dodecyl, and cyclohexyl. Further, the alkenyl group represented by R ¹ is preferably a linear alkenyl group or a C 1 to 5 alkenyl group,
These alkenyl groups may be substituted (for example, a hydroxy group, a halogen atom, etc.), such as vinyl, 1-propenyl, 2-propenyl, 1,3-butadienyl, 2-pentenyl, 3-hydroxy-1 -propenyl, 2-chloro-2-propenyl, and other groups. Furthermore, the aryl group represented by R ¹ is preferably a 6-membered carbon ring, and the aryl group may be substituted (for example, an amino group, a methoxy group, a halogen atom, etc.), such as phenyl, p -aminophenyl, p-methoxyphenyl, m-carboxyphenyl, -chlorophenyl or p-nitrophenyl. In addition, the alkyl group, alkenyl group, and aryl group represented by R ² in the general formula () are as described above.
This is the same as the alkyl group, alkenyl group, and aryl group having no substituent represented by R ¹ . Specific examples of the compound represented by the general formula () include the following compounds. However, the compounds of the present invention are not limited to these. [Exemplary compound] Compound-1 Compound-2 Compound-3 Compound-4 Compound-5 Compound-6 Compound-7 Compound-8 Compound-9 Compound-10 Compound-11 Compound-12 Compound-13 Compound-14 Compound-15 Compound-16 Compound-17 The method for synthesizing the compound of the present invention will be described below, but other compounds can also be synthesized by a similar method. Synthesis Example 1 (Compound 2) 80 g of ethyl isocyanate was dissolved in 100 ml of dimethylformamide, 90 g of aminoguanidine sulfate was added thereto, and the mixture was heated and stirred at 100° C. for 4 hours. 300 ml of 3N-NaOH aqueous solution was added to the reaction solution, and the mixture was heated under reflux for 1 hour. After cooling, the reaction solution was neutralized with concentrated hydrochloric acid, and 400 ml of water was added and cooled to precipitate crystals.
The crystals have a melting point of 195-8°C). Synthesis Example 2 (Compound 4) 150g of benzyl isocyanate and 200ml of ethanol
Dissolve 160g of aminoguanidine sulfate in this
was added and heated under reflux for 20 hours. Ethanol in the reaction solution is distilled off under reduced pressure, and the residue is
600 ml of 3N-NaOH aqueous solution was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution was neutralized with concentrated hydrochloric acid, and upon cooling, crystals were precipitated. Filter the crystals and add 1000ml of water.
Compound 4 was obtained by recrystallization from
℃). Synthesis Example 3 (Compound 5) 135 g of phenyl isocyanate was dissolved in 150 ml of dimethylformamide, 110 g of aminoguanidine hydrochloride was added thereto, and the mixture was heated and stirred at 100° C. for 4 hours.
600 ml of 2N-NaOH aqueous solution was added to the reaction solution, and the mixture was heated under reflux for 3 hours. After cooling, the reaction solution was neutralized with concentrated hydrochloric acid, and then added with water.
When 400 ml was added and cooled, crystals precipitated. The crystals were collected by filtration and recrystallized from 500 ml of water to obtain Compound 5 (melting point: 267° to 268°C). Synthesis Example 4 (Compound 8) 128g of N-guanidinothiourea hydrochloride was added to 3N-
It was dissolved in 400 ml of NaOH aqueous solution and heated under reflux for 3 hours. After cooling, the reaction solution was neutralized with concentrated hydrochloric acid, and upon cooling, crystals were precipitated. The crystals were collected by filtration and recrystallized from 400 ml of water to obtain Compound 8 (melting point: 302° to 304°C). The amount of the compound represented by the above general formula () varies depending on the type of organic silver salt used, the type of reducing agent, etc., but is based on 1 mole of organic silver salt.
The range is preferably from 0.001 mol to 10 mol, particularly preferably from 0.005 mol to 0.5 mol. General formula () In the formula, R ³ represents a hydrogen atom, a hydroxy group, or an alkyl group, an alkenyl group, an aryl group, or an alkoxy group each of which may have a substituent, Y represents a sulfonyl group or a carbonyl group, and X ⁰ represents a sulfur atom. or = N-R ³¹ ,
R ³¹ represents a hydrogen atom, an amino group, or an alkyl group, an aryl group, or an alkenyl group, each of which may have a substituent. In the general formula (), as the alkyl group which may have a substituent, both R ³ and R ³¹ are linear, branched or cyclic and have 1 to 20 carbon atoms; Specific examples include methyl group, ethyl group, propyl group, butyl group, bentyl group, hexyl group, heptityl group, nonyl group, undecyl group, tridecyl group, pentadecyl group, heptadecyl group, inadecyl group, isobentyl group,
Examples include tert-butyl group, cyclohexyl group, benzyl group, 3-hydroxypropyl group, dichloromethyl group, and trifluoromethyl group. In addition, examples of the alkenyl group which may have a substituent include a vinyl group, a 1-propenyl group, where both R ³ and R ³¹ are linear and have 2 to 12 carbon atoms;
2-propenyl group, 1,3-ptadienyl group, 2
-pentenyl-3-hydroxy-1-propenyl group, 2-chloro-2-propenyl group and the like. Further, as the aryl group which may have a substituent, both R ³ and R ³¹ are phenyl group, p-nitrophenyl group, m-chlorophenyl group, m-carboxyphenyl group, p-methoxyphenyl group, p- Examples include aminophenyl group and pyridyl group. In addition, examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, an isopropoxy group, a tert-ptoxy group, a 2-nitroethoxy group,
Examples include 2-chloroethoxy group. Specific examples of the compound represented by the general formula () include the following compounds. Compound-18 Compound-19 Compound-20 Compound-21 Compound-22 Compound-23 Compound-24 Compound-25 Compound-26 Compound-27 Compound-28 Compound-29 Compound-30 Compound-31 Compound-32 Compound-33 Compound-34 Compound-35 Compound-36 Compound-37 Compound-38 Compound-39 Compound-40 Compound-41 Compound-42 Compound-43 Compound-44 Compound-45 Compound-46 Compound-47 These compounds are 4-substituted-3-amino-5
It can be easily synthesized by reacting -mercapto-1,2,4-triazole or 2-amino-5-mercapto-1,3,4-thiadiazole with an acid chloride or an acid anhydride. Synthesis Example 5 (Compound 20) 4-allyl-3-amino-5-mercapto-
Dissolve 15.6 g (0.1 mol) of 1,2,4-triazole in 40 ml of propionic acid, and add propionic anhydride.
16.0g (0.125mol) was added and stirred at 130°C for 2 hours. When the reaction solution was cooled to room temperature, crystals were precipitated. The crystals were collected by filtration and recrystallized from 150 ml of acetonitrile to obtain 7.8 g of compound-3 (melting point: 124°~
126℃). Synthesis Example 6 (Compound 26) 4-allyl-3-amino-5-mercapto-
15.6 g (0.1 mol) of 1,2,4-triazole was dissolved in 50 ml of pyridine, and 14.7 g (0.105 mol) of benzoyl chloride was added dropwise to this solution while keeping the temperature below 10°C. Thereafter, the temperature of the reaction solution was raised to 25° C., stirred for 1 hour, and then 300 ml of ethanol was added and cooled to precipitate crystals. The crystals were collected by filtration and washed with ethanol to obtain 12.0 g of Compound 9. (Melting point 165° to 166°C). Synthesis Example 7 (Compound 33) 4-allyl-3-amino-5-mercapto-
15.6 g (0.1 mol) of 1,2,4-triazole was dissolved in 50 ml of pyridine, and 12.6 g (0.11 mol) of methanesulfonyl chloride was added dropwise to this solution while keeping the temperature below 10°C. After that, the temperature of the reaction solution was increased to 30℃.
After stirring for 1 hour, 300 ml of ethanol was added and cooled to precipitate crystals. The crystals were collected by filtration and washed with ethanol to obtain Compound 16 (melting point: 122°~
124℃). Synthesis Example 8 (Compound 38) 2-Amino-5-mercaptothiadiazole
Dissolve 17.8 g (0.1 mol) in 40 ml of acetic anhydride and add 90
After heating to ℃ for 15 minutes, 200 ml of ethanol was added and cooled to precipitate crystals. The crystals were collected by filtration and recrystallized from ethanol to obtain compound 21 (melting point:
mp282°~285°C). The amount of the compound represented by the above general formula () varies depending on the type of organic silver salt used, the type of reducing agent, etc., but is based on 1 mole of organic silver salt.
The range is preferably from 0.001 mol to 10 mol, particularly preferably from 0.005 mol to 0.5 mol. Also general formula () In the formula, R ⁴ is a hydrogen atom, an alkyl group, or

[Formula] R ⁵ is an alkyl group or

Represents [formula]. Here R ⁴¹ is a hydrogen atom, an amino group or

[Formula], and R ⁵¹ is an alkyl group. Said R ⁴ , R ⁵ , R ⁴¹
The number of carbon atoms in the alkyl group represented by and R ⁵¹ is not particularly limited, but is practically 1 to 18 carbon atoms. Examples of the compound represented by the general formula () include the following compounds, but are not necessarily limited to these examples. (Exemplary compound) Compound-48 Compound-49 Compound-50 Compound-51 Compound-52 Compound-53 Compound-54 Compound-55 Compound-56 Compound-57 Compound-58 Compound-59 These compounds can be easily synthesized by reacting a 4-substituted thiosemicarbazole with an acid anhydride or hydrochloride, or by reacting a substituted benzoylhydrazine with a thioisocyanate compound. Synthesis Example 9 (Exemplary Compound 49) 10 g of 4-phenylthiosemicarbazide was added to 80 c.c.
of pyridine, cooled with ice, and slowly added 8 g of propionyl chloride to the solution. Subsequently, the mixture was stirred for 1 hour while cooling with ice. The above mixed solution is poured into ice water to form crystals, which are collected by filtration. The crystals collected by filtration are placed in 80 c.c. of 10% caustic soda solution and heated on a water bath for 2 hours. Then, it is cooled and acidified with hydrochloric acid, and the precipitate is collected by filtration. The precipitate is recrystallized from ethanol to obtain needle-like crystals. Melting point 177℃. Synthesis Example 10 (Exemplary Compound 53) 9 g of 4-ethylthiocarbazide was mixed with 50 c of pyridine.
c., and gradually add 10 g of flopionyl chloride to the above solution while stirring and cooling on ice. The subsequent operations are performed in the same manner as in Pre-Synthesis Example 9. The formed crystals are recrystallized with water to obtain 6 g of needle-shaped crystals with a melting point of 148°C. Synthesis Example 11 (Exemplary Compound 56) p-acetamidobenzoylhydrazine 12.5g
Dissolve in 100c.c. of ethanol and add 10c.c. of ethylthioisocyanate. The mixture is heated under reflux for 2 hours, cooled to precipitate, collected by filtration, and 20 c.c. of 10% caustic soda is added. The solution is again heated to reflux on a water bath for 2 hours. After cooling, the precipitate was acidified with hydrochloric acid, collected by filtration, and re-crystallized from ethanol to obtain 9 g of needle-like crystals. Melting point 244-245℃. The amount of the compound represented by the general formula () used is 0.0001 to 1 mol per 1 mol of the organic silver salt.
The amount used varies considerably depending on the type of compound applied, the material used for the photosensitive material, and the processing temperature.
The above range is practically sufficient. Furthermore, the general formula () In the formula, R ⁶ and R ⁷ may be hydrogen atoms, alkyl groups, or substituted. It is a phenyl group. Next, specific examples of the compound represented by the general formula () include the following compounds, but the present invention is not limited thereto. (Exemplary compound) Compound-60 Compound-61 Compound-62 Compound-63 Compound-64 Compound-65 Compound-66 The above compounds are generally listed in the Journal of the American Chemical Society.
The American Chemical Society) 1917.39 volume,
It can be synthesized by the method on page 1335. Synthesis Example 12 (Exemplary Compound 60) Dissolve 5 g of benzalazine in 150 c.c. of glacial acetic acid,
Add 10g of Rodankari, heat in a hot water bath for 30 minutes, and then cool. The precipitated crystals are collected by filtration and recrystallized from alcohol. Obtain 5 g of crystals with a melting point of 188°C. Synthesis Example 13 (Exemplary Compound 63) 6.8g of hydrazine hydrochloride and 19.6g of rhodanpotash water
Dissolve to 100c.c. and add 20c.c. of glacial acetic acid. This was stirred under ice cooling. This includes valeroaldehyde 17.2
Gradually add g. After the addition is complete, the mixture is stirred at that temperature for 2 hours. The precipitated crystals are collected by filtration and recrystallized from glacial acetic acid. 9 g of crystals with a melting point of 174° C. are obtained. Synthesis Example 14 (Exemplary Compound 65) 104g of hydrazine hydrochloride and 196g of rhodanpotash were added to water.
Dissolve in 500c.c. and add 150c.c. of glacial acetic acid.
This was stirred under ice-cooling, and propylaldehyde was added to it.
Gradually drip 116 g. After the addition, the mixture was further stirred on ice for 2 hours. The precipitated crystals are collected by filtration and recrystallized from a mixed solution of methanol and water. 165 g of crystals are obtained with a melting point of 186-187°C. The appropriate amount of the compound represented by the general formula () is 0.0001 to 1 mol per 1 mol of the organic silver salt. (Thermal Solvent Used in the Present Invention) Next, the heat solvent characteristically used in the present invention is solid at storage temperature such as room temperature, and is heated at or below the heat treatment temperature such as heat development, but slightly lower than that. It is a non-hydrolyzable organic material that exhibits a mixed melting point with other components and becomes a liquid at a temperature higher than the storage temperature, e.g. 80°C or higher, and it is a non-hydrolyzable organic material that becomes a liquid in a solution state compared to a solid state. The movement and diffusion of substances becomes easier. The heat solvent used in the present invention includes polyglycols described in US Pat. No. 3,347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax, monostearin, For example, compounds with a high dielectric constant having -SO ₂ -, -CO- groups described in US Pat. Polar substance described in No. 3667959, lactone of 4-hydroxybutanoic acid, methylsulfinylmethane,
Tetrahydrothiophene-1,1-dioxide, 1,10- described in RD December 1976 issue, pages 26-28
Decanediol, methyl anisate, biphenyl suberate or, for example, pentaerythol described in Japanese Patent Application No. 82064/1988 are preferably used. It is preferable to use a sufficiently large amount of the heat solvent within a range that does not interfere with the film-forming properties of the film-forming binder used in the photosensitive material, and the amount added should be below the upper limit determined by the film-forming properties of the binder used. In this case, it is used in an appropriate amount after adjusting the characteristics with other photosensitive materials. The upper limit of the amount added is approximately 1:1 by weight with respect to the binder. (Dye-providing substance used in the present invention) Heat-transferable dye-providing substances preferably used in the present invention include, for example, JP-A No. 57-186744 and Japanese Patent Application No. 57-18674.
122596, 57-160698, 57-126054, etc., in which a diffusible dye is released by oxidative coupling with a reducing agent, and JP-A-57
-179840, Japanese Patent Application No. 57-10248, and other types that release dyes by redox are all useful. Furthermore, among both types of dye-providing substances, those that release sublimable dyes can also be preferably used. Therefore, the present invention includes the following general formulas (), (), (), (), and () separately proposed and disclosed by the applicant for other purposes such as Japanese Patent Application No. 57-122596.
Compounds represented by are useful. General formula () A-B-C General formula () General formula () General formula () General formula () The dye-providing substance (CPM) represented by the above general formula will be sequentially explained below. In the general formula () representing the dye-providing substance used in the present invention, the general formula () ABC is represented by the following formula: where A represents a coupler residue. B represents a simple bond or a divalent bonding group. C represents a dye residue or a dye precursor residue. Particularly preferred dye-providing substances in the present invention are:
A in the general formula () is represented by the following general formula (i) or (ii). General formula (i) General formula (ii) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
R ₈ is 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 24 carbon atoms), such as a methyl group, an ethyl group, or a t-butyl group. group, s-octyl group, pentadecyl group, cyclohexyl group, trifluoromethyl group, penzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group, etc.),
Acyl groups (e.g. acetyl group, tetradecanoyl group, bivaloyl group, benzoyl group, etc.), alkyloxycarbonyl groups (e.g. methoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, p -Tolyloxycarbonyl group, α-
naphthoxycarbonyl group, etc.), alkylsulfonyl group (e.g., methylsulfonyl group, etc.), arylsulfonyl group (e.g., phenylsulfonyl group, etc.), carbamoyl group (e.g., methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl -N-dodecylcarbamoyl group, phenylcarbamoyl group, etc.), acylamino group (e.g. n-butylamide group, β-phenoxyacetamide group, β-methanesulfonamide acetamide group, β-methoxyacetamide group, etc.), alkoxy group ( Preferably, it is an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group, an ethoxy group, an octadecyloxy group, etc.),
It represents a sulfamoyl group (eg, memorsulfamoyl group, phenylsulfamoyl group, etc.), a sulfamino group (eg, methylsulfamino, tolylsulfamino), or a hydroxy group. However, preferably at least one of R ₁ , R ₂ , R ₃ and R ₄ and at least one of R ₅ , R ₆ , R ₇ and R ₈ are ballast groups that reduce thermal diffusivity, for example, It has a group containing a hydrophilic group such as a sulfo group, a carboxy group, or a hydroxy group, or a group containing an alkyl group and having 8 or more carbon atoms. Furthermore, at least one set of R ₁ and R ₂ , R ₃ and R ₄ , and at least one set of R ₅ and R ₆ , and R ₆ and R ₇ are bonded to each other, and saturated or unsaturated 5- 6
It may form a membered ring. In the general formula (), B represents a simple bond, ie, a case in which a coupler residue and a sublimable dye residue or a sublimable dye precursor residue are directly bonded, or a divalent bonding group. Examples of divalent bonding groups include -O-, -S-,

【formula】

[Formula] -N=N-,

【formula】

【formula】

【formula】

[Formula] etc. In the general formula (), the sublimable dye residue represented by C is preferably a monoazo dye residue, an anthraquinone dye residue, a nitrodiphenylamine dye residue, or the like. The sublimation temperature of these sublimable dyes is 70℃~300℃
℃, preferably 80℃ to 250℃. There are various methods for measuring sublimation temperature, and the measured value may differ depending on the method. In the present invention, methods for evaluating the fastness of dyes can be used, and among them, the values measured by the drying test of the hot pressing test (JIS L0850) have shown a good correlation with the transfer characteristics. Specific examples of dye-providing substances that are particularly effective in the present invention are shown below, but the present invention is not limited thereto. (Exemplary dye-donating substance) Next, in the general formula () representing the dye-providing substance used in the present invention, the general formula () In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or a substituent that does not substantially impede the sublimability of the dye to be formed, and R ₁₁ and
R ₁₂ may be bonded together to form a 5- to 6-membered carbocycle or heterocycle. Y represents a ballast group which has a molecular size and shape suitable for imparting thermal non-diffusivity or non-sublimation property, and which can be eliminated by reaction with an oxidized product of a color developing agent. This type of compound is of the type that forms sublimable dyes by oxidative coupling with reducing agents;
It has a ballast group as an active site substituent. Typical specific examples of the compound represented by the above general formula () are listed below. (Exemplary dye-donating substance) Next, in the general formula () representing the dye-providing substance used in the present invention, the general formula () In the formula, G is OH or NHR ₁₃ (where R ₁₃ is a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, lauryl, hexadecyl, etc.), and D represents an image-forming dye, such as azo, azomethine, anthraquinone, naphthoquinone, nitro, styryl, quinophthalone, triphenylmethane, phthalocyanine dye, etc., but preferably These dye moieties are preferably oil-soluble dyes that do not contain carboxyl groups or sulfo groups. and E
is a group of atoms necessary to form a benzene ring, a naphthalene ring, a heterocycle, etc. (these atomic groups are carbon atoms,
(nitrogen atom, oxygen atom). Although the above-mentioned heterocycles are not particularly limited, representative examples include rings such as indole, carbazole, benzofuran, dibenzofuran, phenothiazine, and phenoxazine. In addition, Ball represents an immobilizing group present on a ring such as a benzene ring, a naphthalene ring, or a heterocycle.
This immobilizing group has at least one carboxyl group, sulfo group, or a salt thereof, and when m (described below) is 2, they may be the same or different groups. m and n are each 1
or represents an integer of 2. Furthermore, L has an atomic number of 1~
8 is a divalent organic group, Nu represents a nucleophilic group, and this nucleophilic group and the electrophilic center (carbon atom indicated by * in the general formula) generated by oxidation during development etc. may form a 5- to 12-membered ring, preferably a 5- to 8-membered ring, particularly preferably a 5- and 6-membered ring. Examples of the organic group include a methylene group having 1 to 8 carbon atoms, an oxamethylene group, an aminomethylene group, a sulfonyl group, a carbonyl group, an amide group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a phenylene group, etc. be able to. Further, the nucleophilic group represented by the above-mentioned Nu is a nucleophilic group consisting of a hydroxyl group, an amino group, a carboxyl group, a sulfo group, and the like. A preferred compound represented by the above general formula () can be represented by the following general formula (iii) or (iv). General formula (iii) General formula (iv) In the formula, D, L, Nu, Ball and m are D, L, Nu, Ball and m in the general formula ().
and represent the same radical and number, respectively. It is estimated that the compound represented by the above general formula () releases NH ₂ SO ₂ --D having a dye moiety through an oxidation reaction and an intramolecular nucleophilic reaction during thermal development. More specifically, for example, the above general formula (iii)
In the case of the compound represented by , it is thought that NH ₂ SO ₂ --D having a dye moiety is released by oxidation reaction and intramolecular nucleophilic reaction as shown below. Typical specific examples of the compound represented by the above general formula () are described below. (Exemplary dye-donating substance) Next, the general formula () representing the dye-providing substance used in the present invention loses its release properties when it is oxidized. In other words, it indicates a positive-acting dye-donating substance, and the general formula () In the formula, X is an oxidizable nucleophilic substituent, preferably a hydroxyl group. X ₁ is a hydroxyl group or an amino group (any of a primary amino group, secondary amino group, or tertiary amino group) substituted at the ortho position or para position (preferably para position) with respect to the above X , preferably a hydroxyl group. Further, E ₁ represents an atomic group necessary to form a benzene ring or a naphthalene ring, and the benzene ring and naphthalene ring may further have a substituent, and in this case, the substituent includes a carboxyl group, Sulfo group or salt thereof, halogen atom (preferably chlorine atom, bromine atom, iodine atom), alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, such as methyl group, ethyl group, t-butyl group) group, s-octyl group,
pentadecyl group, cyclohexyl group, trifluoromethyl group, penzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group, etc.), acyl group (e.g. acetyl group, tetradecanoyl group, pivaloyl group) group, benzoyl group, etc.), alkyloxycarbonyl group (e.g., methoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, p-tolyloxycarbonyl group, α-naphthoxycarbonyl group, etc.) ), alkylsulfonyl groups (e.g., methylsulfonyl groups, etc.), arylsulfonyl groups (e.g., phenylsulfonyl groups, etc.), carbamoyl groups (e.g., methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group) group, phenylcarbamoyl group, etc.), acylamino group (e.g. n
-butyramide group, β-phenoxyacetamide group, β-methanesulfonamide acetamide group,
β-methoxyacetamide 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 (such as memorsulfamoyl group, phenyl group, etc.), (e.g., sulfamoyl group), sulfoamino group (e.g., methylsulfoamino, tolylsulfoamino), etc. In addition to these groups, carboxyl groups, sulfo groups, salts thereof, or hydrophilic groups derived from these groups can be mentioned. may be substituted with a functional group. _R14
represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms and optionally having a substituent) or an aryl group (preferably an aryl group having 6 to 24 carbon atoms optionally having a substituent); where Z represents an oxygen atom or a sulfur atom. Further, J is a divalent linking group, specifically R ₁₅ | -N- group, -O-, or -S-, and R ₁₅ in this case is a hydrogen atom, an alkyl group (preferably 5 carbon atoms represents the following alkyl group or alkoxyalkyl group) or aryl group (preferably an optionally substituted phenyl group), and J
-D ₁ represents a thermodiffusible dye residue (preferably a sublimable dye residue). m ₁ is 0 or a positive integer (preferably 0, 1 or 2). At least one of the substituents and substituent R ₁₄ on the benzene ring or naphthalene ring of the thermal dye-providing substance has a molecular size and/or a size sufficient to substantially immobilize the dye-providing substance against thermal diffusion.
or a ballast group having a shape. Preferred ballast groups include sulfonic acid,
Examples include carboxylic acid, phosphoric acid, etc., groups derived from these acids, and alkyl groups and aryl groups substituted with these groups. Also, if the dye-providing substance itself is substantially immobile to heat, it is not necessary to introduce such a ballast group. Particularly when the thermal diffusion of the released dye is sublimation, a dye donor material without a ballast group is itself substantially non-sublimable and often does not require the introduction of a ballast.
Typical specific examples of the compound represented by the above general formula () are described below. (Exemplary dye-donating substance) Furthermore, the general formula () representing the dye-donating substance used in the present invention represents a dye-releasing reducing agent that can release a dye upon oxidation. In the formula, X ₂ and X ₃ are each a hydrogen atom, a hydroxyl group, or an amino group (primary amino group,
Either a secondary amino group or a tertiary amino group may be used,
It also includes amino groups substituted with hydroxyl groups, sulfonamide groups, etc.), and at least one of X ₂ and X ₃ is a hydroxy group or an amino group. E ₂ and E ₃ each represent an atomic group necessary to form a benzene ring or a naphthalene ring, and these rings may further have a substituent. In this case, the substituent includes a carboxyl group, a sulfo group, etc. or salts thereof, halogen atoms (preferably chlorine atom, bromine atom, iodine atom), alkyl groups (preferably alkyl groups having 1 to 24 carbon atoms, such as methyl group, ethyl group, t-butyl group, s -octyl group, pentadecyl group, cyclohexyl group, trifluoromethyl group, benzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group, etc.), acyl group (e.g. acetyl group, tetradeca (noyl group, pivaloyl group, benzoyl group, etc.),
Alkyloxycarbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group, etc.),
Aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-tolyloxycarbonyl group,
α-naphthoxycarbonyl group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, etc.),
Arylsulfonyl group (e.g., phenylsulfonyl group), carbamoyl group (e.g., methylcarbamoyl group, butylcarbamoyl group, tetradecylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group, phenylcarbamoyl group, etc.),
Acylamino group (e.g. n-butyramide group, β
- phenoxyacetamide group, β-methanesulfonamide acetamide group, β-methoxyacetamide group, etc.), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy group, ethoxy group, octadecyloxy group) Such),
Examples include a sulfamoyl group (eg, methylsulfamoyl group, phenylsulfamoyl group, etc.), a sulfoamino group (eg, methylsulfamino, tolylsulfamino), and hydroxy. R ₁₆ represents a hydrogen atom, an alkyl group (which may be substituted, preferably a methyl group, an ethyl group, a methoxymethyl group, or a methoxyethyl group), or an aryl group (preferably a phenyl group), and R ₁₆ | -N- The group D ₂ represents the residual amount of thermodiffusible dye. The compound represented by the above general formula () is the above-mentioned
At least one of the substituents on the ring formed by E ₂ and E ₃ is a ballast group having a molecular size and/or shape sufficient to render the compound thermally non-diffusible. Although preferred, a ballast group is not necessarily required if the dye released from the compound is sublimable or if the dye transfer is done in a gaseous state, since the compound is substantially non-sublimable. . Particularly preferred ballast groups include acids such as sulfonic acid, carboxylic acid, and sulfinic acid, and hydrophilic substituents such as groups derived from these acids. Typical specific examples of the compound represented by the above general formula () are described below. (Exemplary dye-donating substance) In order to incorporate the above-mentioned dye-providing substance according to the present invention into the heat-developable photosensitive layer of a color thermal transfer photosensitive material, for example, US Pat.
As described in No. 2322027, it can be dissolved and contained in a high boiling point solvent. Furthermore, in the above dispersion method, the dye-providing substance 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, and n-nonylphenol, and examples of low boiling point solvents include methyl acetate, butyl propionate, and cyclopropionate. hexanol,
Diethylene glycol monoacetate is known. These solvents may be used alone or in combination, and the dye-donating substance dissolved in the solvent may be anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan. It can be mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as a monolauric acid ester, emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and added to the heat-developable photosensitive layer. The amount of each of the above-mentioned dye-providing substances to be used varies depending on the characteristics thereof and the combination with the light-sensitive materials used together, and is ultimately determined by experiments from a practical standpoint. Incidentally, the amount is 0.01 to 10 mol, preferably 0.1 to 0.2 mol, per mol of organic silver salt. (Photosensitive silver halide used in the present invention) Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, Examples include silver chloroiodobromide. The photosensitive silver halide can be prepared by any method known in the photographic field, such as a single-jet method or a double-jet method, but in particular, in the present invention, a silver halide gelatin emulsion is prepared. Light-sensitive silver halide emulsions prepared according to techniques including the following give favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include gold sensitization, sulfur sensitization, and gold sensitization.
Various methods such as sulfur sensitization and reduction sensitization can be used. The silver halide in the above-mentioned light-sensitive emulsion may have coarse or fine grains, but the preferred grain size is about 1.5 microns to about 0.001 microns, more preferably about 0.5 microns to about 0.001 microns in diameter.
It is 0.01 micron. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. Furthermore, as another method for preparing photosensitive silver halide,
It is also possible to cause a photosensitive silver salt-forming component to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming components used in this preparation method include inorganic halides, such as
Halide represented by MXn (where M represents an H atom, _NH4 group or a metal atom, and X is
Cl, Br or I, n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, and lead. , antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium,
Examples include platinum and cerium. ), halogen-containing metal complexes (e.g. K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ ,
(NH ₄ ) ₂ IrCl ₆ , (NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ ,
(NH ₄ ) ₃ Rucl ₆ , (NH ₄ ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr ₆
etc.), onium halides (e.g., quaternary ammonium halides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethylosphonium bromide) quaternary phosphonium halides such as benzylethyl methyl bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform, bromoform carbon tetrabromide, 2-bromo-2 - methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalic acid imide, N-bromoacetamide, N-
-Iodosuccinimide, N-bromphthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4 , 4-dimethylhydantoin, etc.) and other halogen-containing compounds (eg, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.001 to 1.0 per mol of organic silver salt.
mol, preferably 0.01 to 1.3 mol. In addition, blue-sensitive silver halide emulsions, green-sensitive silver halide emulsions, which are used in each layer of the color thermal transfer photosensitive material of the present invention, that is, the heat-developable blue-sensitive layer, the heat-developable green-sensitive layer, and the heat-developable red-sensitive layer, respectively. A red-sensitive silver halide emulsion can be obtained by adding various spectral sensitizing dyes to the silver halide emulsion. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridineoxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may contain hydroxyalkyl groups, sulfoalkyl groups, carboxyalkyl groups, aminoalkyl groups or enamine groups capable of forming fused carbocyclic or heterocyclic rings. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. The merocyanine dye may have an acidic nucleus other than the above-mentioned basic nucleus, such as a thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolidinedione nucleus, valpituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, or pyrazolone nucleus. good. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc., such as U.S. Pat.
A supersensitizing additive that does not absorb visible light as described in the specification of No. 2937089 can be used in combination. The amount of these dyes added is from 10 ^-4 mol to 1 mol per mol of silver halide or silver halide forming component. More preferably, it is 10 ⁻⁴ mol to 10 ⁻¹ mol. (Organic silver salt used in the present invention) Examples of organic silver salts used in the color thermal transfer photosensitive material of the present invention include Japanese Patent Publication Nos. 43-4924 and 44-
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 described in specifications such as No. 3330633 and No. 4168980, such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, etc. Also, aromatic silver carboxylates, such as silver benzoate, silver phthalate, etc., and silver salts having an imino group, such as silver benztriazole, silver saccharin, silver phthalazinone, etc.
Silver salts of compounds having mercapto or thione groups such as silver phthalimide, such as silver 2-mercaptobenz-oxazole, silver mercaptooxadiazole, silver mercaptobenzthiazole, silver 2-mercaptobenzimidazole, 3-mercapto-phenyl-1, 2,4-triazole silver, and also 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene silver, 5-methyl-7
-Hydroxy-1,2,3,4,6-pentazaindene silver and the like. Also RD16966, same
Silver compounds such as those described in British Patent No. 16907, British Patent No. 1590956, and British Patent No. 1590957 can also be used. Among these, silver salts having an imino group such as benztriazole silver salts are preferred, and examples of benztriazole silver salts include alkyl-substituted benztriazole silvers such as methylbenztriazole silver, bromo-benztriazole silver, chlorbenztriazole silver, etc. Halogen substituted benztriazole silver such as triazole silver, amide substituted benztriazole silver such as 5-acetamidobenztriazole silver, also British Patent No. 1590956;
Compounds described in each specification of No. 1590957, such as N
- [6-chloro-4-N (3,5-dichloro-4
-Hydroxyphenyl)imino-1-oxo-5
-Methyl-2,5-cyclohexadien-2-yl]-5-carbamoylbenztriazole silver salt, 2-benztriazole-5-ylazo-4
-Methoxy-1-naphthol silver salt, 1-benztriazole-5-ylazo 2-naphthol silver salt, N-benztriazol-5-yl-4-
Examples include (4-dimethylaminophenylazo)benzamide silver salt. Further, nitrobenztriazoles represented by the following general formula () and benztriazoles represented by the following general formula (XI) can be advantageously used. General formula () In the formula, R ⁹ represents a nitro group, and R ¹⁰ and R ¹¹ may be the same or different and each represents a halogen atom (e.g., chlorine, bromine, iodine), a hydroxy group, a sulfo group, or a salt thereof (e.g., sodium salt,
potassium salt, ammonium salt), carboxy group or its salt (e.g. sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or carbamoyl group, sulfamoyl group, alkyl group (which each may have a substituent) For example, methyl group, ethyl group, propyl group), alkoxy group (e.g. methoxy group, ethoxy group), aryl group (e.g. phenyl group) or amino group,
r represents an integer of 0 to 2, and s represents an integer of 0 to 1. Examples of substituents for the carbamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents for the sulfamoyl group include a methyl group, ethyl group, and acetyl group. Examples of substituents include carboxy groups and ethoxycarbonyl groups; examples of substituents for aryl groups include sulfo groups and nitro groups; examples of substituents for alkoxy groups include carboxy groups and ethoxycarbonyl groups; Examples of the substituent include an acetyl group, a methanesulfonyl group, and a hydroxy group. The compound represented by the general formula () is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds. For example, 4-nitrobenzotriazole silver, 5
-Nitrobenzotriazole silver, 5-nitro-6
-Chlorbenzotriazole silver, 5-nitro-6
-Methylbenzotriazole silver, 5-nitro-6
-Methoxybenzotriazole silver, 5-nitro-
7-phenylbenzotriazole silver, 4-hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-7-nitrobenzotriazole silver, 4
-Hydroxy-5,7-dinitrobenzotriazole silver, 4-hydroxy-5-nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-
Nitro-6-methylbenzotriazole silver, 4-
Sulfo-6-nitrobenzotriazole silver, 4-
Carboxy-6-nitrobenzotriazole silver,
5-Carboxy-6-nitrobenzotriazole silver, 4-carbamoyl-6-nitrobenzotriazole silver, 4-sulfamoyl-6-nitrobenzotriazole silver, 5-carboxymethyl-6-
Silver nitrobenzotriazole, Silver 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole, Silver 5-nitro-7-cyanobenzotriazole, Silver 5-amino-6-nitrobenzotriazole, Silver 5-nitro-7-(p-nitrophenyl) )
Benzotriazole silver, 5,7-dinitro-6-
Examples include silver methylbenzotriazole, silver 5,7-dinitro-6-chlorobenzotriazole, and silver 5,7-dinitro-6-methoxybenzotriazole. General formula (XI) In the formula, R ¹² has a hydroxy group, a sulfo group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), or a substituent. ^R13 represents a halogen atom (e.g., chlorine, bromine, iodine), a hydroxy group, a sulfo group, or a salt thereof (e.g., sodium salt, potassium salt). , ammonium salts), carboxy groups or salts thereof (e.g., sodium salts, potassium salts, ammonium salts), nitro groups, cyano groups, or alkyl groups that may each have substituents (e.g., methyl groups, ethyl groups, (propyl group), aryl group (eg, phenyl group), alkoxy group (eg, methoxy group, ethoxy group), or amino group, p is 1 or 2, and q is an integer of 0 to 2. Further, examples of substituents for the carbamoyl group in R ¹² include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. can. Furthermore, as a substituent for the alkyl group in R, for example, a carboxy group, an ethoxycarbonyl group, etc., as a substituent for an aryl group, for example, a sulfo group, a nitro group, etc., and as a substituent for an alkoxy group, for example, a carboxy group, Examples of the ethoxycarbonyl group and the substituent of the amino group include an acetyl group, a methanesulfonyl group, and a hydroxy group. Specific examples of the organic silver salt represented by the general formula (XI) include the following compounds. For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-hydroxybenzotriazole silver,
Silver sulfobenzotriazole, silver 5-sulfobenzotriazole, silver benzotriazole-4-sodium sulfonate, silver benzotriazole-5
-Sodium sulfonate, silver benzotriazole-4-potassium sulfonate, silver benzotriazole-5-potassium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, 4-carboxybenzotriazole Silver, 5-carboxybenzotriazole silver, benzotriazole silver-
Sodium 4-carboxylate, silver benzotriazole-sodium 5-carboxylate, silver benzotriazole-4-potassium carboxylate, silver benzotriazole-5-potassium carboxylate, silver benzotriazole-4-ammonium carboxylate, 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-methoxy Benzotriazole silver, 4-hydroxy-5
-Silver nitrobenzotriazole, silver 4-hydroxy-5-cyanobenzotriazole, silver 4-hydroxy-5-aminobenzotriazole, silver 4-hydroxy-5-acetamidobenzotriazole, silver 4-hydroxy-5-benzenesulfonamidobenzotriazole 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-
Acetamide benzotriazole 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 acid, 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-
4-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-7-sulfobenzotriazole silver and the like can be mentioned. These compounds may be used alone or in combination of two or more. The method for preparing the organic silver salt according to the present invention will be described later, but the organic silver salt according to the present invention may be isolated and used by dispersing it in a binder by an appropriate means, or it may be used by dispersing it in a binder by an appropriate means. The silver salt may be prepared in a binder and used as is without isolation. The amount of organic silver salt used is 0.05 g per 1 m ² of support.
-10.0g, preferably 0.2g - 2.0g. (Reducing agent used in the present invention) Examples of reducing agents used in the color thermal transfer photosensitive material of the present invention include, for example, US Pat. No. 3,531,286;
Same No. 3761270, Same No. 3764328, also RD12146,
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 RD15108, RD15127 and JP-A-56-27132, etc. can be used to advantage. In addition, Japanese Patent Application Publication No. 186744, Patent Application No. 57-122596
In the case of heat-transferable dye-providing substances described in No. 57-160698, No. 57-126054, etc., the above-mentioned p.
- Phenylenediamine-based or lower developing agents can be advantageously used. In this case, a diffusible dye is released or formed by oxidative coupling of the reducing agent with these thermally transferable dye-providing substances. Also, Japanese Patent Application No. 163234/1983, Japanese Patent Application No. 135628/1983
CD precursors such as those described in U.S. Pat. No. 54-79035, U.S. Pat. Other color methods include, for example, JP-A-57
―179840, Patent Application No. 102487, etc., or characteristically There is a color method using the above, and in addition to the above-mentioned reducing agents, the following reducing agents used in the color method can be used. In other words, color methods other than those mentioned above include those using the SDB method, and those in which the dye is bleached with a reducing agent in the unexposed (unconsumed) area, such as those used in Japanese Patent Application Laid-Open No. 1986-
No. 10582, Publication No. 52-105822, U.S. Patent No.
Specification No. 4235957, RD18137, RD15126, RD18137
There are methods such as 15227 and 15676, and the following reducing agents can be used. That is, phenols (for example, p-phenylphenol, p-methoxyphenol, 2,6-di-
tert-butyl-p-cresol, N-methyl-p
- aminophenol, etc.), sulfonamide phenols (e.g. 4-benzenesulfonamide phenol, 2-benzenesulfonamide phenol, 2,6-dichloro-4-benzenesulfonamide phenol, 2,6-dibromo-4-(p-
toluenesulfonamide) phenol, etc.), or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols (e.g. 1,1 '-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.), methylenebisphenols (e.g., 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol-
α,α-bis(2-hydroxy-3,5-di-
tert-butylphenyl)methane, α-phenyl-
α,α-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane 1,1-bis(2-hydroxy-3,5-dimethylphenyl)
-2-methylpropane, 1,1,5,5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,2-bis(4-hydroxy-3,5- dimethylphenyl)
Propane, 2,2-bis(4-hydroxy-3-
methyl-5-tert-butylphenyl, 2,2-bis(4-hydroxy-3,5-di-tert-butylphenyl)propane, etc.), ascorbate, 3
- Examples include pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. Further, the reducing dye compound itself can be used as a reducing agent, and for example, dye developers such as those disclosed in processes such as RD15126 and RD17706 can also be used. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of organic acid silver salt, photosensitive silver salt, and other additives used, but is usually 0.05 mol to 1 mol of organic acid silver salt. The amount ranges from 10 mol, preferably from 0.1 mol to 3 mol. (Other materials used in the present invention) Various dye release aids can be used in the color thermal transfer photosensitive material of the present invention. A dye release aid is one that can nucleophilically attack a dye-donating substance oxidized by an organic silver salt and release a diffusible dye, and a base, a base release agent, or a water release compound is used. It will be done. Among these dye release aids, bases or base release agents are particularly useful for not only promoting dye release, but also for promoting the redox reaction between the organic silver salt and the dye-donor. Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[ Examples include p-(dialkylamino)phenyl]methane. U.S. Pat. No. 2,410,644 describes tetramethylammonium betaine iodide and diaminobutane dihydrochloride, and U.S. Pat. No. 3,506,444 describes organic compounds containing amino acids such as urea and 6-aminocaproic acid, which are useful. A base release agent releases a basic component upon heating. An example of a typical base release agent is British Patent No.
Described in No. 998949. Preferred base releasing agents are salts of carboxylic acids and organic bases; useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid, and useful bases include guanidine, piperidine, morpholine, p-toluidine, 2-picoline, and the like. Guanidine trichloroacetic acid, described in US Pat. No. 3,220,846, is particularly useful. Aldonamides described in JP-A-50-22625 are preferably used because they decompose at high temperatures to produce bases. A water-releasing compound is a compound that decomposes during thermal development to release water and replaces a compound with a vapor pressure of 10 ^-6 Torr or more at a temperature of 100 to 200°C. These compounds are particularly known for transfer printing of textiles, and are known as NH ₄ Fe described in Japanese Patent No. 88386-1986.
(SO ₄ ) _{2.12H 2} O etc. are useful. These dye release aids can be used in a wide variety of ways. 1/100 to 10 times molar ratio to silver,
In particular, it is preferably used in a range of 1/20 to 2 times. Furthermore, in addition to the above-mentioned components, various additives may be added to the color thermal transfer photosensitive material of the present invention, if necessary. For example, as a development accelerator, U.S. Pat.
Alkali release agents described in the specifications of 4060420, 4088496, 4207392 or RD15733, 15734, 15776, etc., Japanese Patent Publication No. 45-12700
Organic acids described in US Pat. No. 3,667,959, non-aqueous polar solvent compounds having -CO-, -SO ₂ -, -SO- groups, melt formers described in US Pat. No. 3,438,776, US Patent No.
There are polyalkylene glycols described in Specification No. 3666477 and Japanese Patent Application Laid-open No. 19525-1987. In addition, as a color toning agent, for example, JP-A-46-4928, JP-A-46-4928;
No. 6077, No. 49-5019, No. 49-5020, No. 49-
No. 91215, No. 49-107727, No. 50-2524, No. 50
-67132, 50-67641, 50-114217, 50-67641, 50-114217, 50-67641, 50-114217,
No. 52-33722, No. 52-99813, No. 53-1020, No.
No. 53-55115, No. 53-76020, No. 53-125014,
No. 54-156523, No. 54-156524, No. 54-156525
No. 54-156526, No. 55-4060, No. 55-4061
Publications such as No. 55-32015 and West German patent no.
2140406, 2147063, 2220618, U.S. Patent No. 3080254, 3847612, U.S. Pat.
Phthalazinone, phthalicide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in specifications such as No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. 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 mixtures of one or more of these with imidazole compounds, or acids such as phthalic acid, naphthalic acid, etc. Examples include mixtures of at least one acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. Also, Patent Application No. 57-73215, No. 57-76838
The 3-amino-5-mercapto-1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles described in the specification of the present invention are also effective. Further, as anti-fogging agents, for example, Japanese Patent Publication No. 11113/1986, Japanese Patent Publication No. 90118/1972, Japanese Patent Publication No. 49/1989
No. 10724, No. 49-97613, No. 50-101019, No. 49
-No. 130720, No. 50-12331, No. 51-47419, No. 51-47419, No.
No. 51-57435, No. 51-78227, No. 51-104338,
No. 53-19825, No. 53-20923, No. 51-50725,
No. 51-3223, No. 51-42529, No. 51-81124,
Publications such as No. 54-51821 and No. 55-93149, as well as British Patent No. 1455271, US Patent No. 3885968,
Same No. 3700457, No. 4137079, No. 4138265,
Mercury salts, which are compounds described in specifications such as West German Patent No. 2617907, or oxidizing agents (for example, N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic oxides, persulfates, etc.), or acids and their salts (e.g., sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g., mercapto compound-releasing compounds,
thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthione, polysulfide compounds, etc.), and other compounds such as oxazoline, 1,2,4-triazole, and phthalimide. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45228, No. 50-119624, No. 50-120328, No.
Halogenated hydrocarbons described in Publication No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Methylsulfonylbenzothiazole, 2,4-bis(tripromomethyl)-
Examples include 6-methyltriazine. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be performed using a sulfur-containing compound as described in each publication of No. 50-77034. Furthermore, U.S. Patent Nos. 3301678 and 3506444
The isothiuronium-based stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
The actuator stabilizer precursor described in No. 4,060,420, etc. may also be contained. In addition to the above-mentioned components, the color thermal transfer photosensitive material of the present invention may further include binders, spectral sensitizing dyes, antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, spreading agents, etc. Various additives, coating aids, etc. are added. Various binders can be used in the color thermal transfer photosensitive material of the present invention, and suitable binders include hydrophilic or hydrophobic water binders depending on the purpose. For example, proteins such as gelatin and gelatin derivatives, cellulose derivatives, polysaccharites such as dextran, natural substances such as gum arabic, latex-like vinyl compounds that increase the dimensional stability of photosensitive materials, and synthetic polymers such as the following. includes. Suitable synthetic polymers include U.S. Pat. No. 3,142,586;
Same No. 3193386, Same No. 3062674, Same No. 3287289,
Examples include those described in each specification of the same No. 3411911. Useful polymers include alkyl acrylates, methacrylates, acrylic acids,
Examples include water-insoluble polymers made of sulfoalkyl acrylate or methacrylate. Suitable polymeric substances include polyvinyl butyral, polyacrylamide cellulose acetate,
butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose polyvinyl chloride, chlorinated rubber polyisobutylene,
Examples include butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzylcellulose, cellulose acetate, cellulose fropionate, and cellulose acetate phthalate. Among these polymers, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, and cellulose acetate butyrate are particularly preferred. Moreover, if necessary, two or more kinds may be used in combination. The amount of binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts per part of organic silver salt for each photosensitive layer. The layers containing the above components and other layers according to the present 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, polyethylene film, polyethylene terephthalate film,
Examples include plastic films such as polycarbonate films, glass, paper, and metals such as aluminum. Furthermore, baryta paper, resin-coated paper, and water-resistant paper can also be used. (Layer structure used in the present invention) In addition to the photosensitive layer, the color thermal transfer photosensitive material used in the practice of the present invention includes various layers such as an overcoat polymer layer, an undercoat layer, a packing layer, an intermediate layer, and a filter layer. It can be set up accordingly. Various mordants for dye images can be used as the image-receiving layer in the color thermal transfer photosensitive material of the present invention.
The image-receiving layer may also be a separate image-receiving element comprising the image-receiving layer on a suitable support, or the image-receiving layer may be a single layer that is part of the color thermal transfer photosensitive material element described above. Good too. If desired, an opacifying layer can be included in the photosensitive material element, such layer reflecting the desired degree of radiation, such as visible light, that can be used to observe the dye image in the image-receiving layer. It is used to make The opacifying layer can contain various reagents to provide the necessary reflection, such as titanium dioxide. The above-mentioned mordant depends on the physical properties of the dye to be mordant,
A useful mordant can be determined depending on the transfer conditions and the combination with other components and materials used in the photosensitive material. Examples of useful mordants include polymers containing ammonium salts described in U.S. Pat. No. 3,709,690. can be mentioned. For example, in poly(styrene-co-N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride), the ratio of styrene to vinylbenzylammonium chloride is from 1:4 to 4:1, preferably 1:1. Similar to the color thermal transfer photosensitive layer according to the present invention, coating solutions for the protective layer, intermediate layer, undercoat layer, back layer, image-receiving layer, and other layers are prepared, and can be applied using the dipping method, air knife method, or curtain coating method. Alternatively, photosensitive materials can be prepared by various coating methods such as the hopper coating method described in U.S. Pat. Therefore, two or more layers can be coated simultaneously. (Practical use of the present invention) Various exposure means can be used for the color thermal transfer photosensitive material according to the present invention. The latent image is exposed to radiation including visible light. Obtained by imagewise exposure. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, and CRT beams, can be used as the light source. The original drawing can be used as a drawing, etc. Of course, a linear image may be a photographic image with stages.Also, printing from the original drawing may be contact printing, reflection printing, or enlargement printing.Also, images projected by a video camera or the like or image information sent from a television station may be used. directly to CRT or
It is also possible to print the image on a color thermal transfer photosensitive material using a contact lens or a lens. 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,
You can use LEDs that emit green, red, and infrared light, and design layers that are sensitive to these lights to emit yellow, magenta, and cyan dyes, respectively. That is, the green-sensitive layer contains a dye-donating material that releases a yellow dye, the red-sensitive layer contains a dye-donating material that releases a magenta dye, and the infrared-sensitive layer contains a dye-donating material that releases a cyan dye. All you have to do is make sure that it stays that way. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light-receiving element such as a CCD, storing it in the memory of a computer, etc., and applying so-called image processing to process this information as necessary, this image information is reproduced on a CRT and used as an image-like light source. or based on the processed information.
There is also a method of exposing by directly emitting light from three types of LEDs. After exposure of the color thermal transfer photosensitive material of the present invention, the obtained latent image is, for example, 0.3 seconds to 120 degrees at about 80° to 250°C.
The photosensitive material can be developed by heating the entire surface in seconds. As long as the temperature falls within the above range, both high and low temperatures can be used by increasing or shortening the heating time. Especially about 110℃~200℃
are useful, and the heating means may be a hot plate, iron, hot roller or the like. In the present invention, the specific method for forming a color image by development is thermal diffusion transfer of a diffusible dye, and for this purpose, the color thermal transfer photosensitive material is
As described above, from a photosensitive layer containing at least silver halide, an organic silver salt, a reducing agent thereof, a dye-providing substance, and a binder on a support, and an image-receiving layer capable of receiving a diffusible dye formed by the photosensitive layer. configured. The above-mentioned photosensitive layer and image-receiving layer may be formed on the same support, or may be formed on separate supports. The image receiving layer can be peeled off from the photosensitive layer. For example, after imagewise exposure of a color thermal transfer photosensitive material, an image-receiving layer can be superimposed on the photosensitive layer and uniformly heat-developed. Further, after the color thermal transfer photosensitive material is subjected to imagewise exposure and uniform heat development, an image-receiving layer may be placed thereon and the dye may be transferred by heating at a temperature lower than the development temperature. (Example) Next, the present invention will be specifically explained using an example. First, a method for preparing the organic silver salt used in the Examples will be described. <Preparation of 4-hydroxybenzotriazole silver salt> Dissolve 17 g of silver nitrate in 225 c.c. of water and stir while stirring.
Aqueous ammonia was added dropwise, and the addition was stopped when the formed silver oxide was completely dissolved. The above ammoniacal silver nitrate solution was added to a solution of 13.8 g of 4-hydroxybenzotriazole (synthesized according to the method described in Japanese Patent Application No. 1065/1982) in 175 cc of ethanol and stirring. The reaction solution was filtered, washed with water and methanol, and dried to obtain 23.2 g of white crystals. <Preparation of 5-nitrobenzotriazole silver salt> 18.0 g (0.11 mol) of 5-nitrobenzotriazole was dissolved in 300 ml of ethanol, and a solution of 17 g (0.10 mol) of silver nitrate dissolved in 100 ml of water was added dropwise to this solution. Stir for a minute. The resulting crystals were filtered and washed with 100 ml of ethanol to obtain 26.4 g of silver nitrobenzotriazole. <Preparation of silver benzotriazole> Dissolve 12 g of benzotriazole in 250 ml of isopropyl alcohol, and add 17 g of silver nitrate to this solution.
A solution dissolved in 50 ml was added dropwise at 40°C and stirred for 30 minutes. The resulting product was filtered and washed with 100 ml of ethanol, yielding 20.5 g of silver benzotriazole. <Preparation of silver 4-sulfobenzotriazole> 22 g of 4-sulfobenzotriazole and 100 ml of water
A solution of 17 g of silver nitrate dissolved in 200 ml of water was added to this solution and stirred for 30 minutes. The resulting crystals were filtered and washed with 100 ml of water to obtain 26 g of the desired product. <Preparation of silver salt dispersion> To each of the above-described organic silver salts, 76.7 cc of a 25% water-soluble polyvinyl butyral aqueous solution (Sekisui Chemical Co., Ltd., Eslec W-201), 370 c.c. of water, and 224 c.c. of methanol were added.
was added and pulverized and dispersed in an alumina ball mill to obtain the following silver salt dispersion. Silver salt dispersion Silver salt A 4-Hydroxybenzotriazole silver B 5-nitrobenzotriazole silver C Benzotriazole silver D 4-Sulfobenzotriazole silver Example 1 Coupler (outside of the present invention) was added to silver salt dispersion A25c.c. 0.93 g each of the following couplers 1 and 2) and CPM-5 which provides the diffusible dye of the present invention,
0.42 g of the following developer, 5 c.c. of a 25% aqueous solution of water-soluble polyvinyl butyral, 10 c.c. of water, and a silver iodobromide emulsion with an average particle size of 0.05 μm prepared by a conventional method in terms of silver. 36 mg was added, and after dispersion in a Pall mill, it was coated on photographic baryta paper using a wire bar so that the wet film thickness was 55 μm. (Sample No. 1 to 3) The dried sample was exposed to 30,000 CMS through a step wedge. On the other hand, 1.40 g of cellulose diacetate (degree of acetylation approximately 60%) per square meter was applied on ivory paper.
I coated it and made receiver paper. Japanese paper was sandwiched between the coated surface of the exposed sample and the coated surface of the image receiving paper, and the surface temperature was 180°C.
After pressing and heating with an iron at ℃ for 30 seconds, the sample and receiver paper were separated. The image on the support was bleached and fixed by a conventional method, and the maximum and minimum image densities (reflection densities) of the resulting dye image were measured. Additionally, the maximum and minimum densities of the image diffused into the image-receiving layer were measured. The results are shown in Table-1.

[Table] As shown above, when using a dye-donating substance (No.
3) Although a transferred image can be obtained on the image-receiving layer, its density is insufficient for practical use. When the density of a cyan image obtained by coupling on a support is measured, it is found that the dye-providing substance is less likely to undergo a coupling reaction with conventional couplers (Coupler 1, Coupler 2). Example 2 Samples Nos. 1 to 12 were prepared in the same manner as in Example 1, except that a hot solvent and Compound 1 of the present invention were added. In addition to the same evaluation as in Example 1, the silver amount (maximum, minimum) produced by heat development was measured by fluorescent X-ray analysis after desilvering by a conventional fixing process. The results are shown in Table-2. As can be seen from the results in Table 2, dye-providing substances (CPMs) have lower silver development efficiency (dissolved material development) during thermal development than ordinary couplers.
It can be seen that the coupling reaction between the oxidized reducing agent produced by silver development and the coupler (CPM) is inefficient. In this system, the hot solvent is
It can be seen that the effect of promoting silver development, which was known in conventional monochrome thermal development systems, actually promotes the coupling reaction, and that sufficient image density can be obtained even with the use of CPM, which has low reactivity. However, systems using hot solvents have a high minimum concentration (capri) and cannot be put to practical use. In a system without a hot solvent, Compound-1 exhibits some development accelerating effect as was known in conventional monochrome thermal development systems, but when used in the CPM and thermal solvent system of the present invention, the development acceleration effect caused by the hot solvent increases. The unique effect of drastically reducing the minimum concentration without any loss in effectiveness was observed. Therefore, even when using a weakly reactive CPM by using a hot solvent and the compound-1 of the present invention,
An image having a sufficiently high maximum density and a sufficiently low minimum density can be obtained.

[Table] Example 3 Example 2 except that B was used as the organic silver salt dispersion
Samples No. 13 to 20 were prepared in the same manner as above, and
We looked at the effects of CPM, a hot solvent, and a mercaptotriazole derivative (MTA).

【table】

[Table] Example 4 Example 2 except that C was used as the organic silver salt dispersion
Samples Nos. 21 to 28 were prepared using the same method as above, and the variation range of effects depending on the type of thermal solvent was shown. It is assumed that all the hot solvents exhibit similar effects by adjusting the amount added.

【table】

[Table] Example 5 Example 2 except that D was used as the organic silver salt dispersion
Samples Nos. 29 to 38 were prepared using the same method as above, and the variation range of effects depending on the type of mercaptotriazole derivative (MTA) according to the present invention was shown.
It can be seen that both are effective and have an optimum addition amount.

【table】

Claims (1)

[Scope of Claims] 1. In a color thermal transfer photosensitive material in which a dye image is formed on an image-receiving layer by heat development, at least a photosensitive silver halide, a diffusible dye, or a diffusible dye precursor is provided on a support. dye-providing substance, thermal solvent and the following general formula (), (), () or ()
A color thermal transfer photosensitive material characterized by containing a compound represented by: General formula () General formula () General formula () General formula () (In the general formula (), R ¹ is a hydrogen atom, an amino group, or an alkyl group that may each have a substituent,
Represents an alkenyl group or an aryl group, R ²
represents a hydrogen atom, an amino group, or an alkyl group, an alkenyl group, or an aryl group having no substituent. In the general formula (), R ³ is a hydrogen atom, a hydroxy group, or an alkyl group, alkenyl group, aryl group, or alkoxy group, each of which may have a substituent. Y ⁰ represents a sulfonyl group or a carbonyl group, X ⁰ represents a sulfur atom or N—R ³¹ , where R ³¹ is a hydrogen atom, an amino group, or an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent. represents a group. In the general formula (), R ⁴ represents a hydrogen atom, an alkyl group, or [Formula] R ⁵ represents an alkyl group or [Formula]. Here, R ⁴¹ is a hydrogen atom, an amino group or [Formula], and R ⁵¹ is an alkyl group. In addition, in the general formula (), R ⁶ and R ⁷ are hydrogen atoms,
It is an alkyl group or a phenyl group which may be substituted. )