JPH0624157A - Coloring matter donating material for thermal transcription - Google Patents

Abstract

PURPOSE:To improve the transcription, image concentration, sensitivity, and storage stability of a coloring matter donating layer by incorporating more than one kind of pyrazoloazole azomethyne coloring matter expressed by a given general formula into the donating layer. CONSTITUTION:More than one kind of pyrazoloazole azomethyne coloring matter expressed by a formula is incorporated into a thermal transcription coloring matter donating layer. In the formula, R<1>. R<2> are respectively selected from alkyl group; R<3>-R<6> from hydrogen atom, alkyl group, halogen atom, and alkoxy group; and R<7> from aryl group having a substituent at its ortho position. Za-Zc are -N= or -CR<8>= (R<8>: H, alkyl, aryl, acyl, alkoxycaronyl, carbamoyl, or aryloxycarbonyl group). R<1>, R<2> are selected from methl and ethyl groups; R<7> from o-chlorophenyl, o-tolyl, o-methoxyphenyl,2,4-dichlorophenyl, 2-methyl-4- chlorophenyl group, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a thermal transfer dye-donor material which has good storage stability, high density and high sensitivity.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is light and compact, noise-free, excellent in operability and maintainability, and easy to colorize. . The thermal transfer recording method is a method in which a thermal transfer dye-providing material in which a heat-fusible ink layer is held on a support is heated by a thermal head to melt the ink and transfer it to an image receiving material (melt transfer method), and thermal transferability. A thermal transfer dye-donor material having a dye-donor layer containing the dye and a binder is heated by a thermal head to transfer only the dye to the image-receiving layer of the image-receiving material for recording (heat transfer method. It is also called a thermal transfer method). The present invention relates to a thermal transfer dye-donor element used in the latter thermal transfer system having this content.
Here, the heat transferable dye means a dye which can be transferred from the thermal transfer dye-providing material to the thermal transfer image-receiving material by sublimation or diffusion in a medium.

However, the heat transferable dyes conventionally used in this system have various restrictions, and very few heat transferable dyes have the required performance. Required performance includes, for example, having preferable spectral characteristics in color reproduction, easy thermal transfer, no discoloration or fading to light or heat, little deterioration by various chemicals,
The sharpness does not easily decrease after image formation, bleed-out of the image with time does not easily occur, retransfer of the image does not easily occur, the thermal transfer dye-donor material is easily prepared, and the storage stability of the thermal transfer dye-donor material is improved. Being excellent. Among these, it is important that the thermal transfer dye-providing material has excellent storage stability. This performance is even more important when sensitizing thermal transfer dye-donor elements to reduce transfer times. When the content or amount of the dye in the dye-donor layer is increased or the content or amount of the binder in the dye-donor layer is decreased to increase the sensitivity of the thermal transfer dye-donor material, the dye is incorporated in the dye-donor layer. Crystallization is likely to occur, and when a conventionally known dye is used, the storage stability of the thermal transfer dye-donor material cannot be satisfied, and there is a limit to speeding up. Examples of magenta dyes include those disclosed in JP-A-64-63194.
The pyrazoloazole-based azomethine dyes described in JP-A Nos. 2-208094 and 4-90384 achieve the above-mentioned various performances at a considerable level.

[0004]

However, the dyes described in JP-A-64-63194 are easily transferred by heat and are excellent in transferability, but on the other hand, the color reproducibility, light fastness, and storage stability are excellent. In that respect, it is unsatisfactory.
Although the color reproducibility and the light fastness of the dye described in No. 4 are improved, it is still a step in terms of light fastness and storage stability. However, some of them are almost satisfactory in terms of light fastness, but since they do not easily transfer heat, they were a step forward in terms of transferability.

Accordingly, an object of the present invention is to provide a thermal transfer dye-donor material which is excellent in transferability and gives a high density image, and to provide a thermal transfer dye-donor material having high sensitivity and shortened transfer time. And to provide a thermal transfer dye-donating material having excellent storage stability, and to provide a thermal transfer dye-donating material having excellent storage stability of an image on an image-receiving paper, and to provide a bright hue. Have,
An object of the present invention is to provide a thermal transfer dye-donor element which gives an image having high fastness to light, heat, humidity, air and chemicals.

[0006]

The objects of the invention have been accomplished by the following thermal transfer dye-donor elements. A thermal transfer dye-donor material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer contains at least one pyrazoloazole azomethine dye represented by the following general formula (I). And a thermal transfer dye-providing material.

[0007]

[Chemical 4]

In the formula (I), R ¹ and R ² represent an alkyl group. R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom,
It represents an alkyl group, a halogen atom, or an alkoxy group. R
⁷ represents an aryl group. Za, Zb, and Zc are -N =
Or it represents a -CR ⁸ =. R ⁸ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group,
It represents a carbamoyl group or an aryloxycarbonyl group. More preferably, R ¹ and R ^{2 in} formula (I) are each independently a methyl group, an ethyl group or an alkyl group having 3 to 10 carbon atoms, and R ⁷ is an o-chlorophenyl group, an o-tolyl group, o A methoxyphenyl group, a 2,4-dichlorophenyl group, or a 2-methyl-4-chlorophenyl group.
Even more preferably, R ¹ and R ^{2 in} the general formula (I) are both methyl groups, and R ⁷ is an o-chlorophenyl group, an o-tolyl group, or an o-methoxyphenyl group. Further, the following thermal transfer dye-donating material preferably achieved the object of the present invention. In a thermal transfer dye-donor material having a dye-donor layer containing a heat transferable dye on a support, the dye-donor layer comprises at least one pyrazoloazole azomethine dye represented by the above general formula (I) and the following general formula: A thermal transfer dye-donor material containing at least one pyrazoloazole azomethine dye represented by (II).

[0009]

[Chemical 5]

In the formula (II), R ⁹ is the following general formula (III),
It is a structure represented by the formula (IV) or (V).

[0011]

[Chemical 6]

In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an amino group, an acyl group or an acyloxy group. Represents an acylamino group, an alkylthio group, an arylthio group, a sulfonylamino group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. R ¹⁵ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (II), R ¹⁰ represents an unsubstituted alkyl group, or an alkyl group, an alkoxy group, an aryloxy group, or an alkyl group substituted with a halogen atom. Formula (II)
Medium, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb, Zc
Represents the same substituent as described in formula (I).

The general formula (I) will be described in detail below. In formula (I), R ¹ and R ² are each independently an alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, amyl, hexyl, octyl), and more preferably R ¹ , R ² are both methyl groups. R
³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom or an alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, n-
Propyl), a halogen atom (chlorine, bromine, fluorine), an alkoxy group (having 1 to 10 carbon atoms, for example, methoxy, ethoxy, isopropoxy), preferably R ³ ,
R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms. R ⁷ is an aryl group having a substituent at the ortho position of the bonding position (having 6 to 10 carbon atoms, for example, o-chlorophenyl, o-methoxyphenyl, o-tolyl, 2,4-dichlorophenyl, 2,4-xylyl, 2, 6-dimethoxyphenyl, 2-methyl-4-chlorophenyl),
Among them, o-chlorophenyl, o-methoxyphenyl, o
-Tolyl is most preferred.

Za, Zb and Zc are -N = or -CR.
Indicates ⁸ =. R ⁸ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an aryloxycarbonyl group. Specific examples of R ⁸ include those described below for R ¹⁶ and R ^{16 ′} . The structure represented by the formula (I) is preferably the following general formula (VI), (VII), (VIII) or (IX).

[0015]

[Chemical 7]

In formulas (VI), (VII), (VIII) and (IX), R
¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are represented by the formula (I)
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same as the above, and specific examples and preferable examples thereof are also the same. R ^{16 in} formulas (VI) and (VII) represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹⁶ is preferably a hydrogen atom, an alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, n-).
Octyl, n-hexyl, n-pentyl, n-pentyl), aryl groups (having 6 to 10 carbon atoms, such as phenyl,
o-chlorophenyl, p-nitrophenyl, m-acetylaminophenyl, 3,5-dichlorophenyl), heterocyclic group (having 3 to 10 carbon atoms, for example, 2-furyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2 -Tetrahydrofuryl). The most preferred R ^{16 in} formulas (VI) and (VII) is an alkyl group.

In the formula (VIII), R ¹⁶ and R ¹⁶ 'each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R ¹⁶ and R ¹⁶ ′ are preferably hydrogen atom, alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, n-propyl,
t-butyl, 2-chloroethyl), aryl group (having 6 to 10 carbon atoms, such as phenyl, m-nitrophenyl, p-
Nitrophenyl, p-tolyl, 3,5-dichlorophenyl), heterocyclic group (having 3 to 10 carbon atoms, for example, 2-pyridyl, 2-furoyl, 2-thienyl, 2-thiazolyl), acyl group (having 2 to 2 carbon atoms) 10, for example, acetyl, piparoyl, benzoyl, o-chlorobenzoyl), carbamoyl (having 1 to 10 carbon atoms, for example, methylcarbamoyl, ethylcarbamoyl, dimethylcarbamoyl), alkoxycarbonyl group (having 2 to 10 carbon atoms, for example, methoxycarbonyl, ethoxy). Carbonyl, isopropoxycarbonyl, n-octyloxycarbonyl), and an aryloxycarbonyl group (having 7 to 10 carbon atoms, for example, phenoxycarbonyl, p-methoxycarbonyl, m-chlorophenoxycarbonyl). R ¹⁶ and R ¹⁶ ′ are more preferably an alkyl group, an aryl group or an acyl group.

In the formula (IX), R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ have the same meanings as R ¹¹ , R ¹² , R ¹³ and R ^{14 in} the formula (II). A preferable one of R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is a hydrogen atom.

Among the structures represented by formulas (VI), (VII), (VIII) and (IX), (VI) is most preferable.

The general formula (II) will be described in detail. In formula (II), R ⁹ is a structure represented by formula (III), (IV) or (V). In formulas (III), (IV) and (V), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom, an alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl). , Methoxyethyl, cyanoethyl),
Aryl group (having 6 to 10 carbon atoms, for example, phenyl, m-
Acetylphenyl, p-methoxyphenyl, tolyl),
A heterocyclic group (having 2 to 10 carbon atoms, for example, 1-piperidyl, 1-morpholyl, 2-furoyl, 2-pyridyl),
Halogen atoms (eg chlorine, fluorine, iodine, bromine),
Alkoxy group (C1-10, for example, methoxy, ethoxy, isopropoxy, methoxyethoxy), aryloxy group (C6-10, for example, phenoxy, p-
Methoxyphenoxy, m-chlorophenoxy), amino group (0 to 10 carbon atoms, amino, methylamino, ethylamino, diethylamino, anilino, N-methylanilino), acyl group (1 to 10 carbon atoms, for example, formyl, acetylbenzoyl, p-toluyl, α-methoxyacetyl), an acyloxy group (having 2 to 10 carbon atoms, for example, acetyloxy, pivaloyloxy, benzoyloxy, m
-Chlorobenzoyloxy), an acylamino group (having 1 to 10 carbon atoms, for example, acetylamino, pivaloylamino,
Benzoylamino, N-methylacetylamino), alkylthio group (1 to 10 carbon atoms, methylthio, ethylthio, isopropylthio), arylthio group (6 to 6 carbon atoms)
10, for example, phenylthio, p-methoxyphenylthio), a sulfonylamino group (having 1 to 10 carbon atoms, for example, methanesulfonylamino, ethanesulfonylamino, toluenesulfonylamino), a sulfonyl group (having 1 to 1 carbon atoms).
0, methanesulfonyl, ethanesulfonyl, toluenesulfonyl), sulfinyl group (having 1 to 10 carbon atoms, for example, methanesulfinyl, ethanesulfinyl, toluenesulfinyl), carbamoyl group (having 1 to 10 carbon atoms, for example, methylcarbamoyl, dimethylcarbamoyl, ethyl) Carbamoyl), sulfamoyl group (having 0 to 1 carbon atoms
0, for example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl), an alkoxycarbonyl group (having 2 to 10 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl, isopropoxycarbonyl), an aryloxycarbonyl group (having 7 to 10 carbon atoms, for example,
Phenoxycarbonyl, p-methoxyphenoxycarbonyl, o-chlorophenoxycarbonyl).

R ¹⁵ is an alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, 2chloroethyl,
t-butyl), an aryl group (having 6 to 10 carbon atoms, for example,
Phenyl, tolyl, m-methoxyphenyl, 2,4,6
-Trimethylphenyl), a heterocyclic group (having 2 to 1 carbon atoms)
0, for example, 2-furyl, 2-pyridyl), an alkoxy group (having 1 to 10 carbon atoms, for example, methoxy, ethoxy, isopropoxy, n-butoxy, methoxyethoxy), an aryloxy group (having 6 to 10 carbon atoms, for example, Phenoxy,
o-chlorophenoxy), an amino group (having 0 to 10 carbon atoms,
For example, amino, dimethylamino, N-methylanilino,
Methylamino). R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are more preferably hydrogen atoms or alkyl groups. In the case of formula (IV), R ¹⁵ is more preferably an alkyl group. Also, R
^In the case of the formula (V), ¹⁵ is preferably an alkyl group, an alkoxy group or an aryloxy group.

In the formula (II), R ¹⁰ represents an unsubstituted alkyl group, or an alkyl group, an alkoxy group, an aryloxy group, or an alkyl group substituted with a halogen atom. Examples of the unsubstituted alkyl group for R ¹⁰ include methyl, ethyl, n-
Propyl, n-butyl, n-pentyl, n-hexyl,
They are n-heptyl and n-octyl. Examples of the alkyl group substituted with an alkyl group include isopropyl, 2-methylhexyl, 1-methylpropyl, 3-methylpentyl,
3-methylhexyl, 3-methylheptyl, 2-methylpentyl, 1-propylbutyl and the like can be mentioned. Examples of the alkyl group substituted with an alkoxy group include 2-methoxyethyl, 2-ethoxyethyl, 3-methoxybutyl, 2-methoxyhexyl and the like. Examples of the alkyl group substituted with an aryloxy group include 2-phenyloxyethyl, 3-phenyloxypropyl, 1
-Phenyloxyethyl, 2- (p-methoxyphenoxy) -ethyl and the like can be mentioned. Examples of the alkyl group substituted with a halogen atom include 2-chloroethyl, 3-
Examples include chloropropyl and 4-chlorobutyl.
Preferred among R ¹⁰ is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or an alkyl group or an alkoxy group. R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb,
Zc is R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or Z of the formula (I).
It is synonymous with a, Zb, and Zc. Specific examples and preferable examples thereof include those described in the formula (I).

Specific examples of dyes used in the thermal transfer dye-providing material of the present invention are shown in Tables 1 to 4. These are for explaining the present invention in detail, and the present invention is not limited by these.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

Specific examples of the compound represented by the general formula (II) will be given below. The present invention is not limited by these compound examples.

[0029]

[Table 5]

Next, an example of synthesizing the dye of the present invention will be shown to explain the synthesizing method. (Synthesis example 1) Synthesis of compound 1

[0031]

[Chemical 8]

917 g of compound a, 8.0 methylene chloride
Liter, 2.25 liters of triethylamine at 20 ° C
While stirring at 1.84 kg of compound b,
721 g of N-bromosuccinimide was divided into 5 portions and added alternately in 30 minutes. Then, the mixture was reacted for 30 minutes. After the reaction was completed, 20 liters of water was added, and the mixture was stirred well to carry out liquid separation. The organic layer was washed with 20 liters of water and the solvent was distilled off under reduced pressure. To the concentrate, 7.0 liter of methanol was added, and the precipitated crystals were filtered and dried to obtain 1.2 kg of Dye 1.
Obtained. mp. 133-134 ° C. λ _max (in ethyl acetate): 530 nm ε _max (in ethyl acetate): 5.34 × 10 ⁴

The heat transfer raw dye of the present invention is contained in the dye-donor layer on the support to prepare a heat-transfer dye-donor material, which is used for image formation in the heat-transfer system. Next, for the case where the heat transfer raw dye of the present invention is used for image formation of a thermal transfer system,
The details will be described below. Usually, three color dyes of yellow, magenta, and cyan are required to form a full-color image. Therefore, the compound of the present invention can be used as a magenta dye, and the other two colors can be selected from known dyes to form a full-color image. For the same color,
The dye of the present invention and a conventionally known dye may be mixed and used. Further, two or more kinds of the dyes of the present invention may be mixed and used in the same color.

The method of using the heat transfer dye of the present invention will be described. The thermal transfer dye-providing material can be used in the form of a sheet or a continuous roll or ribbon. The magenta dye of the present invention and the cyan dye and yellow dye used in combination with the magenta dye are usually arranged on a support so as to form independent regions. For example, a yellow dye area, a magenta dye area, and a cyan dye area are arranged on one support in a frame-sequential or line-sequential manner. Further, it is also possible to prepare three types of thermal transfer dye-donor materials in which the above-mentioned yellow dye, magenta dye, and cyan dye are provided on separate supports, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be carried out sequentially. . The magenta dye of the present invention and each of the cyan dye and yellow dye used in combination with the magenta dye are dissolved or dispersed in a suitable solvent together with a binder resin and applied on a support, or supported by a printing method such as a gravure method. Can be printed on the body.
The thickness of the dye-donor layer containing these dyes is usually about 0.2 to 5 μm, preferably 0.4 to 2 μm as a dry film thickness. The amount of dye applied is 0.03 to 1.0
g / m ² is preferred. Among them, 0.1 to 0.6 g / m ²
Is more preferable.

As the binder resin used together with the above-mentioned dye, any of the binder resins known in the related art for such purpose can be used, and usually has high heat resistance,
Moreover, one that does not interfere with the migration of the dye when heated is selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin (eg polyvinyl alcohol, polyvinyl Acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene) and the like. In the present invention, the dye is, for example, 1% of the total weight of the constituents of the dye-donor layer (mostly the binder and the dye).
It is preferably used in a ratio of 5% to 83%. When a thermal transfer dye-donor element is prepared using a conventionally known dye,
If the proportion of the dye in the dye-donor layer exceeds 50%, the stability of the dye-donor material with time deteriorates, which is not practical. However, surprisingly, the dye used in the present invention does not substantially deteriorate the stability of the dye-donor element with time even when the dye content exceeds 50%. Therefore, when the thermal transfer dye-providing material is required to have high sensitivity, it is preferable to increase the content of the dye so that it exceeds 50%.

In the present invention, any conventionally known ink solvent can be used as the ink solvent for dissolving or dispersing the above dye and binder resin. Any conventionally known support can be used as the support of the thermal transfer dye-providing material. For example polyethylene terephthalate,
Polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide,
Examples thereof include polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 μm.

A slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof.
In order to prevent sticking due to the heat of the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to perform sticking prevention treatment on the side of the support on which the dye-donor layer is not provided. For example, it is preferable to provide a heat resistant slip layer mainly containing a reaction product of polyvinyl butyral resin and isocyanate, an alkali metal salt or an alkaline earth metal salt of phosphoric acid ester, and a filler. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000 and a glass transition point of 80 to 110 ° C.
From the viewpoint of having many reaction sites with isocyanate, the weight% of the vinyl butyral portion is 15 to 40%.
The ones are good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac® manufactured by Toho Kagaku
D720 or the like is used, and it may be used in an amount of about 1 to 50% by weight, preferably about 10 to 40% by weight based on the polyvinyl butyral resin. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The dye-donor element may be provided with a hydrophilic barrier layer for preventing the dye from diffusing toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. Generally good results are gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor element may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired function, but preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate). / 2-aminoethyl methacrylate / -2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear / saturated polyester, for example, Bostic 7650 (M Heart Company, Bostic Chemical Group) Alternatively, a chlorinated high density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the undercoat layer is not particularly limited, but it is usually used in an amount of 0.1 to 2.0 g / m ² .

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material, and heat is applied according to the image information from either side, preferably the back side of the thermal transfer dye-providing material, by heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be similarly transferred. The heating means is not limited to the thermal head, and known means such as laser light (for example, semiconductor laser), infrared flash, and hot pen can be used. In the case of using a laser as the heat source, it is preferable that the thermal transfer dye-providing material contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, the absorbing material converts light energy into thermal energy, transfers the heat to the dye in the immediate vicinity, and is heated to a temperature at which the dye transfers to the thermal transfer image-receiving material. The absorbent material is layered below the dye and / or is mixed with the dye. For a more detailed description of this process, see British Patent 2,083,7.
26A. As the above laser,
Ion gas lasers such as Argon and Krypton,
Metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby and YAG, or 750-87.
Several lasers can be used, such as semiconductor lasers such as gallium-arsenide which emit in the infrared region of 0 nm. Among them, semiconductor lasers are preferable because of their small size, low cost, stability, reliability, durability and ease of modulation. As a specific example, for example, Spectrodiode Lab (Spec
trodiode Labs) laser model SDL-2420-
H2 (registered trademark) or a laser model SLD-304v / w (registered trademark) manufactured by Sony Corporation can be used.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system and the like. It can be used to create prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to.

The thermal transfer image-receiving material used in combination with the thermal transfer dye-providing material of the present invention comprises a support having thereon an image-receiving layer for receiving the dye transferred from the dye-providing material. This image-receiving layer contains a substance capable of receiving a heat-transferable dye having a function of dyeing the heat-transferable dye, which receives the heat-transferable dye transferred from the heat-transfer dye-providing material during printing. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive heat transferable dyes.

(A) having an ester bond: a dicarboxylic acid component such as terephthalic acid, isophthalic acid, succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group); Polyester resin obtained by condensation of tin glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin such as polymethylmethacrylate, polybutylmethacrylate, polymethylacrylate, polybutylacrylate or polymethacrylic acid ester Resin: Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyltoluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used. (B) Those having a urethane bond, such as polyurethane resin. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used.

In the thermal transfer image-receiving material, especially in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned. The image receiving layer of the thermal transfer image receiving material is
A substance capable of receiving the heat transferable dye may be dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a group capable of undergoing a crosslinking reaction by a hardening agent is preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a composition having enhanced dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used for the outermost layer. Using a synthetic resin with a higher point, sticking to the surface, adhering to other substances, or sticking to other substances after transfer, with or without using the minimum amount of high boiling organic solvents or heat solvents It is desirable to have a structure that prevents troubles such as retransfer and blocking with a thermal transfer dye-donor material. The total thickness of the image receiving layer is 0.5 to 50.
μm, particularly 3 to 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm. The image-receiving layer may optionally contain a dye fixing agent. As a dye fixing agent, Japanese Patent Laid-Open No.
-83685 and mordants described in JP-A-1-1
Any of those described in No. 88391 can be used.

The thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer depends on the material
It is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer, or a layer having two or more of these functions, and also serves as an adhesive in some cases. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is a layer which prevents heat applied during thermal transfer from diffusing from the image receiving layer to the support and effectively utilizes the applied heat. The image receiving layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer, etc., which constitute the thermal transfer image receiving material, include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, Fine powder of zinc oxide, lithopone, titanium oxide, alumina or the like may be contained.

The support used for the thermal transfer image-receiving material can withstand the transfer temperature, and can satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, and dent after transfer. Anything can be used. For example, synthetic paper (component paper such as polyolefin-based and polystyrene-based), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin Paper support such as internal paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. A film or sheet that has been treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

A fluorescent whitening agent may be used in the thermal transfer image receiving material. An example of this is K. Veenkataraman's "The Chem.
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples thereof include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostyryl-based compounds, and 2,5-dibenzoxazolethiophene-based compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the present invention, in order to improve the releasability between the thermal transfer dye-donor element and the thermal transfer image-receiving element, in the layers constituting the dye-donor element and / or the image-receiving element, particularly preferably the surface where both materials come into contact. It is preferable to include a release agent in the outermost layer corresponding to the above. As release agents, solid or wax-like substances such as polyethylene wax, amide wax, Teflon powder: Surfactants such as fluorine-based and phosphoric ester-based: paraffin-based, silicone-based, fluorine-based oils, etc. Although any of the above releasing agents can be used, silicone oil is particularly preferable. As the silicone oil, in addition to non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified or epoxy-modified can be used. As an example, refer to "Technical Information of Modified Silicone Oil" issued by Shin-Etsu Silicone Co.
Various modified silicone oils described on page 18B can be mentioned. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone Co., Ltd .: trade name X-22-371).
0) is effective.

The layers constituting the thermal transfer dye-donating material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in the publications are suitable for use. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners (the following hardeners-I
Such),

[0050]

[Chemical 9]

Vinyl sulfone type hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) ethane etc.), N-methylol type hardeners (dimethylol urea etc.) or polymer hardeners (special Kaisho 62-23415
Compounds described in No. 7 and the like).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective. Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794), 4-
Thiazolidone compounds (US Pat. No. 3,352,681
No.), benzophenone compounds (JP-A-56-27)
84, etc., and other Japanese Patent Laid-Open Nos. 54-48535 and 6
There are compounds described in Nos. 2-136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-7556
8 and the compounds described in JP-A-63-199248. Examples of useful anti-fading agents are disclosed in JP-A-62-2.
15272 (125)-(137). An anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be contained in the image-receiving material in advance, or may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. For example, saponin (steroidal), alkylene oxide derivative (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone Polyethylene oxide adducts), glycidol derivatives (for example, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars and the like: alkylcarboxylic acid salts, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphoric acid esters and other carboxy groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups Anionic surfactants containing acidic groups such as:
Amphoteric surfactants such as amino acids, ciminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, sylalkyl betaines, amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, Multiple rings such as imidazolium 4th
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing aliphatic or plural rings can be used. Specific examples of these are disclosed in JP-A Nos. 62-173463 and 62-18345.
No. 7, etc. Further, when dispersing a substance capable of receiving a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent and other hydrophobic compounds in a water-soluble binder, an interface as a dispersion aid is obtained. Preference is given to using activators. For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the matting agent, in addition to the compounds described in JP-A No. 61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-27.
There are compounds described in 4944 and 63-274952.

[0056]

【Example】

Example 1 (Preparation of Thermal Transfer Dye Donor (1-1)) A 6 μm-thick polyethylene terephthalate film having a back surface subjected to a heat-resistant lubrication treatment was used as a support, and a thermal transfer dye having the following composition was formed on the surface of the film. The coating composition for the donor layer was applied by wire bar coating so as to have a dry thickness of 1.5 μm to prepare a thermal transfer dye-providing material (1-1). Coating composition for thermal transfer dye-donating layer: Dye 1 3.0 g Polyvinyl butyral resin (Denkabu Chiral 5000-A manufactured by Denki Kagaku) 3 g Toluene 40 cc Methyl ethyl ketone 40 cc Polyisocyanate (Takenate D1 10N manufactured by Takeda Yakuhin) 0.2 cc In the same manner as above, except that the other dyes shown in Table 1 were used, thermal transfer dye-donor materials of the present invention and comparative thermal transfer dye-donor materials (1-2) to (1-11) were prepared.

(Preparation of Thermal Transfer Image Receiving Material) Synthetic paper having a thickness of 150 μm (YUPO-FPG manufactured by Oji Yuka) as a support.
-150) and a coating composition for an image receiving layer having the following composition on the surface by wire bar coating to a dry thickness of 8
A thermal transfer image receiving material was prepared by coating so as to have a thickness of μm.
Drying was carried out for 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer. Coating composition for image-receiving layer: Polyester resin (Vylon-280 manufactured by Toyobo) 22 g Polyisocyanate (KP-90 manufactured by Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 85 cc Toluene 85 cc Cyclohexanone 15cc

The thermal transfer dye-donor materials (1-1) to (1-10) and the thermal transfer image-receiving material obtained as described above are
The thermal transfer dye-donating layer and the image-receiving layer are superposed so that they are in contact with each other, and a thermal head is used from the support side of the thermal transfer dye-donating material, the output of the thermal head is 0.25 W / dot, the pulse width is 0.15 to 15 milliseconds, Printing was performed under the condition of a dot density of 6 dots / mm, and a magenta dye was dyed imagewise on the image-receiving layer of the image-receiving material. As a result, clear image recording without uneven transfer was obtained. The Status A reflection density of each recorded thermal transfer image-receiving material obtained as described above was measured. In addition, each recorded thermal transfer image-receiving material for 2 weeks, 1
The light fastness of the color image was examined by irradiating it with a fluorescent lamp of 7,000 lux. Measure the Status A reflection density before and after irradiation,
The fastness was evaluated by the ratio (dye residual ratio). The results are shown in Table 6.
Shown in.

Table 6 Thermal transfer dye-providing material Dye No. Maximum density Light fastness Remarks 1-1 1 2.98 78 Invention 1-2 2 2.93 73 〃 1-3 3 2.80 81 〃 1-4 9 2.76 83 〃 1-5 11 2. 82 76 〃 1-6 17 2.75 80 〃 1-7 18 2.71 83 〃 1-8 21 2.75 73 〃 1-9 23 2.70 75 〃 1-10 II-1 2.87 62 Comparison Example 1-11 II-9 2.19 86 〃 1-12 Comparative dye c. 2.54 52 〃

[0060]

[Chemical 10]

As described above, the thermal transfer dye-providing material of the present invention has a high maximum density and a satisfactory level of light fastness, and is capable of achieving both transferability and light stability. Turns out to be better than.

Example 2 The components of the coating composition for a thermal transfer dye-donating layer of Example 1 were changed as follows, and the thermal transfer dye-donating materials (2-1) to (2-11) shown in Table 7 were used. It was made. Coating composition for image-receiving layer-2 Ethyl cellulose 1.5 g Dye 3.0 g Toluene 30 g Methyl ethyl ketone 60 g Asahi Gart AG660 (manufactured by Asahi Glass Co., Ltd.) 0.2 g Silicone oil KF96 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.2 g Polyisocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.) Takenate D110N) 0.5g

When printing was carried out using the image receiving material prepared in Example 1, clear image recording without transfer unevenness was obtained in all cases. In order to examine the storage stability of the prepared thermal transfer dye-donor material, the thermal transfer dye-donating material was stored for 1 week at a temperature of 50 ° C. and a humidity of 80%, and the stability was tested. The evaluation criteria are as follows. Good: Aggregation and crystallization of the dye are not observed even under a microscope. Δ: Aggregation / crystallization of the dye is slightly observed with a microscope. X: Aggregation or crystallization of the dye on one surface is visually observed.

Table 7 Thermal transfer dye-donor elements Dye No. Stability over time Remarks 2-11 ○ Present invention 2-2 2 ○ 〃 2-3 3 ○ 〃 2-4 9 ○ 〃 2-5 11 ○ 〃 2-6 17 △ 〃 2-7 18 ○ 〃 2- 8 21 ○ 〃 2-9 23 △ 〃 2-10 II-1 × Comparative example 2-11 II-8 × 〃

As described above, it can be seen that the thermal transfer dye-providing material of the present invention is excellent in stability over time under heat-forced conditions, even though the content of the dye in the dye-donating layer is high.

Example 3 The dyes of the thermal transfer dye-donor layer coating composition of Example 2 are shown in Table 3.
The thermal transfer dye-donor materials (3-1) to (3
-14) was produced. When printing was performed using the image receiving material produced in Example 1, clear image recording without transfer unevenness was obtained in any case. In order to check the storage stability of the transferred image-receiving material, the temperature was 60 ° C. and the humidity was 70.
% Dye for 2 weeks and the dye was tested for bleedability. The results are shown in Table 8. The evaluation was performed visually, and the sample in which the image was uneven and the density was decreased was determined to have bleeding.

Table 8 Thermal transfer dye Chromium After forced test Remarks Donor material bleed 3-1 Dye 1 2.7 g None Present invention Dye II-1 0.3 g 3-2 Dye 1 2.7 g 〃 〃 Dye II- 2 0.3 g 3-3 Dye 1 2.7 g 〃 〃 Dye II-3 0.3 g 3-4 Dye 1 2.7 g 〃 〃 Dye II-9 0.3 g 3-5 Dye 3 2.7 g 〃 Dye II -1 0.3g 3-6 Dye 3 2.7g 〃 〃 Dye II-2 0.3g 3-7 Dye 18 2.7g 〃 〃 Dye II-9 0.3g 3-8 Dye 21 2.7g 〃 Dye II-3 0.3 g 3-9 Dye 1 2.0 g 〃 〃 Dye 2 1.0 g 3-10 Dye 1 2.0 g 〃 〃 Dye 3 1.0 g 3-11 Dye 1 2.0 g 〃 Dye 11 1. 0g 3-12 Dye 11 2.0g 〃 〃 Dye 17 1.0g 3-13 Dye 1 3.0g Slightly recognized 〃 -14 Dye II-8 3.0 g Comparative Example The image derived from the dye represented by the formula (I) used in the present invention is represented by another dye represented by the formula (I) rather than used by one type. It can be seen that stability is better when used as a mixture with and does not cause bleeding. It is also understood that when the dye represented by the formula (I) and the dye represented by the formula (II) are mixed and used, bleeding does not occur and the stability of the image is high.

[0068]

INDUSTRIAL APPLICABILITY The thermal transfer dye-donor element of the present invention has a high transfer rate and gives high density. Further, even when the content of the dye in the dye-donor layer of the thermal transfer dye-donor material is high, the storage stability of the thermal transfer dye-donor material with time does not decrease. In addition, the light fastness of the image formed by transfer onto the image receiving paper is high.

Claims (4)

[Claims] 1. A thermal transfer dye-donating material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer contains at least one pyrazoloazole azomethine dye represented by the following general formula (I). A thermal transfer dye-providing material characterized by containing. [Chemical 1] In formula (I), R ¹ and R ² represent an alkyl group. R ³ , R
⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group,
Represents a halogen atom or an alkoxy group. R ⁷ represents an aryl group having a substituent at the ortho position of the bonding position. Za,
Zb, Zc represents a -N = or -CR ⁸ =. R
⁸ is a hydrogen atom, an alkyl group, an aryl group, an acyl group,
It represents an alkoxycarbonyl group, a carbamoyl group, or an aryloxycarbonyl group. 2. R ¹ and R ^{2 in} the general formula (I) are each independently a methyl group, an ethyl group or an alkyl group having 3 to 10 carbon atoms, and R ⁷ is an o-chlorophenyl group or an o-tolyl group. ,
The thermal transfer dye-donor element according to claim 1, which is an o-methoxyphenyl group, a 2,4-dichlorophenyl group, or a 2-methyl-4-chlorophenyl group. 3. R ¹ and R ² of the general formula (I) are both methyl groups, and R ⁷ is an o-chlorophenyl group, an o-tolyl group or an o-methoxyphenyl group. Item 1. A thermal transfer dye-providing material according to Item 1. 4. A thermal transfer dye-donor material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer is a pyrazoloazole azomethine dye represented by formula (I) according to claim 1. And a pyrazoloazole azomethine dye represented by the following general formula (II), and a thermal transfer dye-providing material. [Chemical 2] In formula (II), R ⁹ is a structure represented by the following general formula (III), (IV) or (V). [Chemical 3] In the formula, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, amino group, acyl group, acyloxy group, acylamino group. , Alkylthio group, arylthio group, sulfonylamino group, sulfonyl group, sulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group. R ¹⁵ represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (II), R ¹⁰ represents an unsubstituted alkyl group, or an alkyl group, an alkoxy group, an aryloxy group, or an alkyl group substituted with a halogen atom. In the formula (II), R ³ and R
^{4, R 5, R 6,} R 7, Za, Zb, Zc represents the same substituents as those described by the general formula (I).