JPH05286268A - Thermal transfer dye donating material - Google Patents

Abstract

PURPOSE:To obtain a thermal transfer dye donating material excellent in transfer properties and imparting high density by adding a pyrazoloazole azomethine dye having a specific structure. CONSTITUTION:In a thermal transfer dye donating material wherein a dye donating layer containing a thermal transfer dye is provided on a support, at least one kind of a pyrazoloazole azomethine dye represented by formula I [wherein R<1> is a group represented by either one of formulae II-IV (wherein R<8>-R<11> are a hydrogen atom, an alkyl group or the like and R<12> is an alkyl group, an aryl group or the like), R<2> is a 3-8C alkyl group, an alkoxy group, an aryloxy group or a halogen atom, R<3>-R<6> are a hydrogen atom, an alkyl group, a halogen atom or an alkoxy group and Za, Zb, Zc are -N= or -CR<13> (wherein R<13> is a hydrogen atom, an alkyl group or an aryl group)] is added to the dye donating layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a thermal transfer dye-donor element 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 lightweight and compact, has no noise, is excellent in operability and maintainability, and can be easily colorized. .. The thermal transfer recording method is a method in which a thermal transfer dye-donating 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 the 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-donating material to the thermal transfer image-receiving material by sublimation or diffusion in a medium.

[0003]

However, there are various restrictions on the heat transferable dyes conventionally used in this system, and there are very few heat transferable dyes that have the required performances. Required properties include, for example, having preferable spectral characteristics for color reproduction, easy heat transfer, no discoloration or fading due to light or heat, little deterioration by various chemicals, and sharpness after image formation. Is less likely to decrease, bleed-out of the image is less likely to occur over time, retransfer of the image is less likely to occur, a thermal transfer dye-donor material is easy to prepare, and the thermal transfer dye-donor material has excellent storage stability. Is. Among these, it is important that the thermal transfer dye-providing material has excellent storage stability. This performance makes the thermal transfer dye-donor material highly sensitive,
It is even more important when reducing transfer time. 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
Crystallization is likely to occur in the dye-donor layer, 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.

An object of the present invention is to provide a thermal transfer dye-donor element which is excellent in transferability and gives high density. It is an object of the present invention to provide a thermal transfer dye-donor element that has high sensitivity and reduced transfer time. The purpose of the present invention is to
It is an object of the present invention to provide a thermal transfer dye-providing material having excellent storage stability. An object of the present invention is to provide a thermal transfer dye-providing material which has excellent storage stability of an image on a receiving paper.
The object of the present invention is to have bright hues, light, heat, humidity,
It is an object of the present invention to provide a thermal transfer dye-donor element which gives an image having high fastness to the atmosphere and chemicals.

[0005]

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.

[0006]

[Chemical 6]

In the formula (I), R ¹ is the following general formula (II) or (I
It is a structure represented by the formula II) or (IV).

[0008]

[Chemical 7]

In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, amino group, acyl group, 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 ¹² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (I), R ² represents an unsubstituted alkyl group having 3 to 8 carbon atoms, or an alkyl group, an alkoxy group, an aryloxy group, or an alkyl group substituted with a halogen atom. In formula (I), R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. R ⁷ represents an aryl group or a heterocyclic group. Za, Zb, Zc represents a -N = or -CR ¹³ =. R ¹³ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an aryloxycarbonyl group. Further, the following thermal transfer dye-donor elements are preferably achieved. 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 following general formula (I); A thermal transfer dye-donating material comprising at least one pyrazoloazole azomethine dye represented by (V).

[0010]

[Chemical 8]

In the formula (I), R ¹ is represented by the following general formulas (II) and (I
It is a structure represented by the formula II) or (IV).

[0012]

[Chemical 9]

In the formula, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, amino group, acyl group, 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 ¹² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (I), R ² represents an unsubstituted alkyl group having 3 to 8 carbon atoms, or an alkyl group, an alkoxy group, an aryloxy group, or an alkyl group substituted with a halogen atom. In formula (I), R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, a halogen atom or an alkoxy group. R ⁷ represents an aryl group or a heterocyclic group. Z
a, Zb, Zc represents a -N = or -CR ¹³ =. R
¹³ 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. In formula (V), R ¹ , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb and Zc are represented by the formula (I).
R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb,
It is synonymous with Zc. L represents a divalent linking group having 2 to 8 carbon atoms. A is a structure represented by the following general formula (VI).

[0014]

[Chemical 10]

In formulas (VI) and (VII), R ¹⁴ and R ¹⁷ each independently represent an alkyl group or an aryl group. R ¹⁵ , R ¹⁶ , R
¹⁸ and R ¹⁹ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an amino group or a hydroxyl group. R ¹⁴ and R ¹⁵ and / or R ¹⁵ and R
¹⁶ and / or R ¹⁶ and R ¹⁷ and / or R ¹⁷ and R ¹⁸ and / or R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring structure. Among the thermal transfer dye-donor materials containing the dye represented by formula (I) above, the content of the dye in the dye-donor layer is 50% or more based on the weight of the entire composition of the dye-donor layer. More preferably achieved by

The general formula (I) will be described in detail below. In formula (I), R ¹ is a structure represented by formula (II), (III) or (IV). (II), (III),
In the formula (IV), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ 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,
It represents an acyloxy group, 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 ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are preferably hydrogen atom, alkyl group (having 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, methoxyethyl, cyanoethyl), aryl group (having carbon number). 6-10, for example,
Phenyl, m-acetylphenyl, p-methoxyphenyl, tolyl), heterocyclic group (having 2 to 10 carbon atoms, for example,
1-piperidyl, 1-morpholyl, 2-furoyl, 2-
Pyridyl), a halogen atom (for example, chlorine, fluorine, iodine, bromine), an alkoxy group (having 1 to 10 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, methoxyethoxy), aryloxy group (having 6 to 10 carbon atoms, such as phenoxy, p-methoxyphenoxy, m-chlorophenoxy), amino group (having 0 to 10 carbon atoms, amino, methylamino, ethyl). Amino, diethylamino, anilino, N-methylanilino), an acyl group (having 1 to 10 carbon atoms, eg, formyl, acetylbenzoyl, p-toluyl, α-methoxyacetyl), an acyloxy group (having 2 to 10 carbon atoms, eg, acetyloxy, Pivaloyloxy, benzoyloxy, m-chlorobenzoyloxy), acylamino group (having 1 to 10 carbon atoms, for example, acetylamino, pivaloylamino, benzoylamino, N-methylacetylamino), alkylthio group (having 1 to 10 carbon atoms, methylthio,
Ethylthio, isopropylthio), arylthio group (having 6 to 10 carbon atoms, for example, phenylthio, p-methoxyphenylthio), sulfonylamino group (having 1 to 10 carbon atoms,
For example, methanesulfonylamino, ethanesulfonylamino, toluenesulfonylamino), sulfonyl group (having 1 to 10 carbon atoms, methanesulfonyl, ethanesulfonyl, toluenesulfonyl), sulfinyl group (having 1 to 1 carbon atoms).
0, for example methanesulfinyl, ethanesulfinyl,
Toluenesulfinyl), carbamoyl group (C1-C1
10, for example, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl group (having 0 to 10 carbon atoms, for example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl), 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 ¹² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. R ¹² is preferably an alkyl group (having 1 to 1 carbon atoms).
0, for example, methyl, ethyl, isopropyl, 2chloroethyl, t-butyl), aryl group (having 6 to 10 carbon atoms, for example, phenyl, tolyl, m-methoxyphenyl, 2,
4,6-trimethylphenyl), heterocyclic group (C2
-10, 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), amino group (having 0 carbon atoms)
-10, for example amino, dimethylamino, N-methylanilino, methylamino). ^{R 8, R 9, R 10} , R
¹¹ is more preferably a hydrogen atom or an alkyl group.
In the case of formula (III), R ¹² is more preferably an alkyl group.
In the case of the formula (IV), R ¹² is preferably an alkyl group, an alkoxy group or an aryloxy group.

In the formula (I), R ² represents an unsubstituted alkyl group having 3 to 8 carbon atoms, 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 ² include n-butyl, n-propyl, n-pentyl, n-hexyl and 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. 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 ² is an alkyl group having 3 to 6 carbon atoms, which is unsubstituted or substituted with an alkyl group or an alkoxy group.

In the formula (I), R ³ , R ⁴ , R ⁵ and R ⁶ are
Each independently represents a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. R ³ , R ⁴ , R ⁵ , and R ⁶ are preferably a hydrogen atom or an alkyl group (having 1 to 10 carbon atoms, for example,
Methyl, ethyl, n-propyl), halogen atom (chlorine, bromine, fluorine), alkoxy group (carbon number 1-10,
For example, methoxy, ethoxy, isopropoxy).
Among them, R ³ , R ⁴ , R ⁵ , and R ⁶ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.

R ⁷ represents an aryl group or a heterocyclic group. Specific examples of R ⁷ include aryl groups (having 6 to 1 carbon atoms).
0, for example, phenyl, o-chlorophenyl, p-methoxyphenyl, m-chlorophenyl, 3,5-dichlorophenyl), a heterocyclic group (having 3 to 10 carbon atoms, for example, 2-
Pyridyl, 3-pyridyl, 4-pyridyl, 2-furyl,
2-thienyl) and the like. As R ⁷ , an aryl group is preferable to a heterocyclic group. Among them, the aryl group in which the ortho position is substituted is most preferable.

Za, Zb and Zc are -N = or -CR.
Indicates ¹³ =. R ¹³ 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 ¹³ include those mentioned for R ³ , R ⁴ , R ⁵ and R ⁶ in formula (I). The structure represented by the formula (I) preferably has the following general formulas (VII), (VIII) and (I
X) and (X).

[0022]

[Chemical 11]

R in the formulas (VII), (VIII), (IX) and (X)
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. In the formulas (VII) and (VIII), R ¹³ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ¹³ is preferably a hydrogen atom or 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 preferable one of R ^{13 in} the formulas (VII) and (VIII) is an alkyl group.

In the formula (IX), R ¹³ and R ¹³ '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 ¹³ and R ¹³ ′ 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 ¹³ and R ¹³ ′ are more preferably an alkyl group, an aryl group or an acyl group.

In the formula (X), R ¹⁹ , R ²⁰ , R ²¹ and R ²² have the same meanings as those represented by R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in} the formula (II). Preferred as R ¹⁹ , R ²⁰ , R ²¹ and R ²² are hydrogen atoms.

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

The general formula (V) will be described in detail.
R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb, Z
c is R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ of the formula (I),
It is synonymous with R ⁷ , Za, Zb and Zc. Specific examples and preferable examples thereof include those described in the formula (I).

L represents a divalent linking group having 2 to 8 carbon atoms. The divalent linking group represented by L is an alkylene group,
Arylene group, -O -, - S -, - NR 23 -, - CO
-, - SO ₂ - and, it is preferable that a combination of two or more thereof.

[0029] Among them, an alkylene group or an alkylene group, -O -, - S -, - NR 23 -, - CO -, - SO
A group in which a divalent group selected from _2- is combined is preferable. R ²³ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,
It represents an aryl group or a heterocyclic group.

Of these, the following linking groups are most preferable. -(CR ²⁴ R ²⁵ ) _n- (CR ²⁴ R ²⁵ ) _n -NR ²³ CO--(CR ²⁴ R ²⁵ ) _n -NR ²³ SO ₂ --(CR ²⁴ R ²⁵ ) _n -O-CO-- _{^{(CR 24 R 25) n -O-}} - (CR 24 R 25) n -O- (CR 24 'R 25') n '- - (CR 24 R 25) n -NR 23 CO- (CR 24' R ²⁵ ′)
^{_{n '- - (CR 24 R}} 25) n -NR 23 SO 2 - (CR 24'
R ²⁵ ′) _{n ′} − (n and n ′ are each an integer of 1 to 10) wherein R ²⁴ , R ²⁴ ′, R ²⁵ and R ²⁵ ′ are each a hydrogen atom,
Halogen atom, aminocarbonyl group, alkyl group having 1 to 12 carbon atoms, alkoxy group, aryloxy group, alkoxycarbonyl group, acylamino group, acyloxy group,
Represents. Among them, the alkylene group is most preferable.

A is a structure represented by the general formula (VI). In formula (VI), R ¹⁴ and R ¹⁷ represent an alkyl group.
Specific examples of R ¹⁴ and R ¹⁷ include methyl, ethyl, n-butyl,
Examples include isopropyl and n-octyl. R ¹⁵ ,
R ¹⁶ , R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an amino group or a hydroxyl group. R ¹⁵ ,
R ¹⁶ , R ¹⁸ and R ¹⁹ are preferably a hydrogen atom, an alkyl group (having 1 to 10 carbon atoms such as methyl and ethyl), an aryl group (having 6 to 10 carbon atoms such as phenyl, tolyl, o-chlorophenyl) and alkoxy. Group (C1-10, for example, methoxy, ethoxy, isopropoxy), aryloxy group (C6-10, for example, phenoxy, p-methoxyphenoxy), acylamino group (C2-10,
Examples thereof include acetylamino, pivaloylamino) and amino groups (having 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino and N-methylamino). L in formula (V)
Is bound via any one of R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ . Preferably, it is attached via R ¹⁴ .

The dye of the present invention may have an atomic group having an effect of suppressing fading in the dye molecule. It is particularly preferable when high image fastness is required. An atomic group having an effect of suppressing fading is R ¹ of a dye,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb, Z
It may be bound to any part of c. As the atomic group having the effect of suppressing fading, all those described in JP-A-3-205189 can be used. Specific examples of atomic groups having the effect of suppressing fading are given below.
The present invention is not limited to this.

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

Specific examples of dyes used in the thermal transfer dye-donor element of the invention are described below. These are for explaining the present invention in detail, and the present invention is not limited by these.

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

[0041]

[Chemical 19]

[0042]

[Chemical 20]

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

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

The dye of the present invention is synthesized by oxidatively coupling the following coupler B and the following developing agent C.

[0047]

[Chemical formula 23]

In the above formula, X is a hydrogen atom or a leaving group which is released during the coupling reaction. Of course, coupler B may be its tautomer. Alternatively, the dye of the present invention is synthesized by dehydration condensation of the coupler B and the following compound D.

[0049]

[Chemical formula 24]

In this case, X is a hydrogen atom.

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 2

[0052]

[Chemical 25]

While stirring 160 g of compound E, 1.7 liters of methylene chloride and 286 g of triethylamine at 20 ° C., 57 g of compound F and 24 g of N-bromosuccinimide were alternately added over 10 minutes. Then, the mixture was reacted for 10 minutes, and the same amounts of compound F and N-bromosuccinimide were added over 10 minutes. Perform the above operation 5 times in total,
Compound F285g and N-bromo succinimide 120g were added in total. Then react for 20 minutes, water 1.5
1 liter was added, and the mixture was well stirred to perform liquid separation. The organic layer was washed with 1.5 liters of water and the solvent was distilled off under reduced pressure.
1.5 liters of ethyl acetate and methanol in the crude product 7.
Recrystallization was performed by adding 0 liter. After that, the crystals were filtered, washed thoroughly with methanol, and dried. As a result, 169 g (yield 76%) of dye 2 was obtained. mp. 133-135 ° C. λ _max (in ethyl acetate): 532 nm ε _max (in ethyl acetate): 5.44 × 10 ⁴ liters
mol ^-1・ cm ^-1

The heat transfer raw dye of the present invention is contained in the dye-donor layer on the support to give 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 necessary 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,
You may mix and use the dye of this invention and the conventionally well-known dye. Further, two or more 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 cyan dye and magenta dye of the present invention and the yellow dyes used in combination with the cyan 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 plane-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 different supports, and from these, the thermal transfer of dyes to one thermal transfer image-receiving material can be carried out sequentially. .. The cyan dye and magenta dye of the present invention and each of the yellow dyes used in combination with the 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 resins (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, as the ink solvent for dissolving or dispersing the above dye and binder resin, any conventionally known ink solvent can be used. 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 heat from the thermal head and improve slippage when printing from the back side of the dye-donor material, it is preferable to carry out anti-sticking 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 a 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%.
I like the one. 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. In general, excellent results have been obtained with gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate grafted 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 effect, 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 in accordance with the image information from either side, preferably the back side of the thermal transfer dye-providing material, by means of 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, the semiconductor laser is preferable because of its 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 make 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 coating 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 a heat transferable dye.

(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 polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate 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, Toyon 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 synthetic resin as described above, a mixture or copolymer of these may be used.

In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling point organic solvent or a thermal solvent can be contained as a substance capable of receiving a 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 No. -30247 and No. 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 in a water-soluble binder and carried. 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 a higher dyeing property to a dye by using a high-boiling organic solvent or a thermal solvent, and the glass transition layer is used as the outermost layer. Using a synthetic resin with a higher point, or sticking the surface to other substances, 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 failures 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 preferably in the range of 3 to 30 μm. 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 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 plays a role of preventing 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, and the like, which constitute the thermal transfer image receiving material, include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, and 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, frictional property, 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 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 of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably the surfaces of both materials contacting each other. It is preferable to add a release agent to the outermost layer corresponding to the above. Solid release agents such as polyethylene wax, amide wax, and Teflon powder: Wax-like substances: Fluorine-based or phosphate-based surfactants: 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, 6-of the technical data of "modified silicone oil" issued by Shin-Etsu Silicone Co., Ltd.
Examples include various modified silicone oils described on page 18B. 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 isocyanate) is emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd. product 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 cured 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),

[0071]

[Chemical formula 26]

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).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. Examples of the antioxidant include chroman compounds, coumarans 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 ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681
No., etc.), benzophenone compounds (JP-A-56-27)
No. 84, etc., and JP-A-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 of transferring from the dye providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

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, prevention of electrostatic charge, acceleration of development and the like. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicones Polyethylene oxide adducts), glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc., nonionic surfactants: alkyl carboxylates, Alkyl sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, and other carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate 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 multiple 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-providing 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. Typical examples of the organic fluoro compound include 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-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 Nos. 4944 and 63-274952.

[0077]

【Example】

Example 1 (Preparation of Thermal Transfer Dye-donating Material (1-1)) A polyethylene terephthalate film (manufactured by Teijin) having a thickness of 6 μm and having a heat resistant slip treatment on the back surface was used as a support, and the following was formed on the surface of the film. The coating composition for the thermal transfer dye-donating layer having the composition is dried by wire bar coating to have a thickness of 1.
A thermal transfer dye-donor material (1-1) was prepared by coating so as to have a thickness of 5 μm. Coating composition for thermal transfer dye-donating layer: Dye 1 3.0 g Polyvinyl butyral resin (Denkabu Chirar 5000-A manufactured by Denki Kagaku) 3 g Toluene 40 cc Methyl ethyl ketone 40 cc Polyisocyanate (Takenate D1 10N manufactured by Takeda Pharmaceutical Co., Ltd.) 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 (1-10) were prepared.

(Preparation of thermal transfer image-receiving material) Synthetic paper having a thickness of 150 μm (YUPO-FPG manufactured by Oji Yuka Co., Ltd.)
-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) obtained as described above and the thermal transfer image-receiving material were
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. The results are shown in Table 1.

Table 1 Thermal transfer dye-providing material Dye No. Concentration Remark 1-1 1 2.75 Present invention 1-2 2 2.80 〃 1-3 3 2.75 〃 1-4 4 2.70 〃 1-5 8 2.80 〃 1-6 17 2. 85 〃 1-7 21 2.85 〃 1-8 25 2.60 〃 1-9 30 2.80 〃 1-10 VI 2.10 Comparative example

As described above, it can be seen that the thermal transfer dye-donor element of the present invention gives a higher density image as compared to the dye V-1 having 9 carbon atoms in the R ² portion.

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 2 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 2 Thermal transfer dye-donor dye No. Stability with time Remarks 2-11 ○ Present invention 2-2 2 ○ 〃 2-3 3 ○ 〃 2-4 4 ○ 〃 2-5 8 ○ 〃 2-6 17 ○ 〃 2-7 21 ○ 〃 2- 8 25 〃 2-9 30 ○ 〃 2-10 VI × Comparative Example 2-11 a × 〃

[0084]

[Chemical 27]

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-donor layer is high. The effect of the dye having 3 to 8 carbon atoms in the R ² portion of the present invention is clear as compared with the comparative dye a in which the R ² portion has 2 carbon atoms and the dye VI having 9 carbon atoms. ..

Example 3 The dyes of the coating composition for the thermal transfer dye-donor layer of Example 2 are shown in Table 3.
The thermal transfer dye-donor materials (3-1) to (3
-10) 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 3. 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 3 Thermal Transfer Dye Color Element After Forced Test Remarks Donor material bleed 3-1 Dye 1 2.7 g None Present invention Dye V-1 0.3 g 3-2 Dye 2 2.7 g 〃 Dye V- 1 0.3 g 3-3 pigment 3 2.7 g 〃 〃 pigment V-2 0.3 g 3-4 pigment 4 2.7 g 〃 〃 pigment V-3 0.3 g 3-5 pigment 8 2.7 g 〃 pigment V -4 0.3g 3-6 dye 17 2.7g 〃 〃 dye V-5 0.3g 3-7 dye 21 2.7g 〃 〃 dye V-6 0.3g 3-8 dye 25 2.7g 〃 〃 dye V-1 0.3 g 3-9 Dye 1 2.0 g 〃 〃 Dye 2 1.0 g 3-10 Dye 2 2.0 g 〃 〃 Dye 3 1.0 g 3-11 Dye 2 2.0 g 〃 Dye 8 1. 0g 3-12 Dye 2 2.0g 〃 〃 Dye 17 1.0g 3-13 Dye 2 3.0g Slightly recognized 〃 3-14 Dye V-1 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 type of formula (I) rather than one type. When used in combination with a dye, bleeding does not occur and stability is better. When the dye represented by the formula (I) and the dye represented by the formula (V) are mixed and used,
High image stability without bleeding. In the first place, the light fastness of the dye is higher in the dye represented by the formula (V) than in the dye represented by the formula (I). Therefore, when high light fastness of the image is required, It is preferable to mix and use the dye represented by (I) and the dye represented by formula (V). On the other hand, when only the dye represented by the formula (V) is used, the transferability is low and bleeding occurs, so that the light fastness is high, but the overall performance is not preferable.

[0088]

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 fastness of the image formed by transfer onto the image receiving paper is high.

Claims (3)

[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 is the following general formula (II), (III) or (I
The structure is represented by the formula V). [Chemical 2] In the formula, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ 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 ¹² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (I), R ² represents an unsubstituted alkyl group having 3 to 8 carbon atoms, an alkyl group, an alkoxy group, an aryloxy group,
It represents an alkyl group substituted with a halogen atom. In formula (I), R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group. R ⁷ represents an aryl group or a heterocyclic group. Z
a, Zb, Zc represents a -N = or -CR ¹³ =. R
¹³ 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. A thermal transfer dye-donating material having a dye-donor layer containing a heat-transferable dye on a support, wherein the dye-donor layer is at least one of pyrazoloazole azomethine dyes represented by the following general formula (I). And a pyrazoloazole azomethine dye represented by the following general formula (V) at least one kind. [Chemical 3] In formula (I), R ¹ is a structure represented by the following general formula (II), (III) or (IV). [Chemical 4] In the formula, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ 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 ¹² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group. In formula (I), R ² represents an unsubstituted alkyl group having 3 to 8 carbon atoms, an alkyl group, an alkoxy group, an aryloxy group,
It represents an alkyl group substituted with a halogen atom. In formula (I), R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, a halogen atom or an alkoxy group. R
⁷ represents an aryl group or a heterocyclic group. Za, Z
b, Zc represents a -N = or -CR ¹³ =. R ¹³ is
It represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an aryloxycarbonyl group. In formula (V), R ¹ , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , Za, Zb, and Zc are R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , Za, Zb, and Z in formula (I).
Synonymous with c. L represents a divalent linking group having 2 to 8 carbon atoms. A has a structure represented by the following general formulas (VI) and (VII). [Chemical 5] In formulas (VI) and (VII), R ¹⁴ and R ¹⁷ each independently represent an alkyl group or an aryl group. R ¹⁵ , R ¹⁶ , R ¹⁸ , and R ¹⁹ are
It represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group or an amino group.
R ¹⁴ and R ¹⁵ and / or R ¹⁵ and R ¹⁶ and / or R ¹⁶ and R ¹⁷ and / or R ¹⁷ and R ¹⁸ and / or R ¹⁸ and R
¹⁹ may combine with each other to form a ring structure. 3. The thermal transfer dye-donor material according to claim 1, wherein the content of the dye in the dye-donor layer is 50% by weight or more based on the total weight of the constituents of the dye-donor layer.