JP2001191649A - Thermal transfer recording material and method for full color printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer recording material which can realize excellent resolution and in-pixel gradation and can hold a recording performance for a long time, by eliminating the faults of a thermal transfer system and an ink jet system, the problem of kogation in particular, while making the best use of the advantages of both of these systems. SOLUTION: The thermal transfer recording material is led to a transfer part having a porous structure by a capillary phenomenon, changed in a state by heating and transferred to an object of transfer opposite to the transfer part. The material contains the dye expressed by the general formula. (Herein a ring A denotes a hetero ring, R1 and R2 a hydrogen atom, an alkyl, an alkenyl, a phenyl and the like and R3 and R4 an electron-attracting group and the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermal transfer recording method,
In particular, the present invention relates to a thermal transfer recording material and a recording method used in a full-color image recording method in which a recording liquid containing a dye is caused to fly from a recording section by selective heating according to image information and is transferred to an opposing photographic paper.

[0002]

2. Description of the Related Art In recent years, as colorization of video cameras, computer graphics, and the like has progressed, the need for colorization of hard copies has rapidly increased. On the other hand, a color hard copy system such as a sublimation thermal transfer system, a melt thermal transfer system, an ink jet system, an electrophotographic system, and a heat-developed silver salt system has been proposed. Among these recording methods, methods for easily outputting high-quality images with a simple apparatus can be broadly classified into a dye diffusion thermal transfer method (sublimation thermal transfer method) and an ink jet method.

Among these recording methods, according to the dye diffusion thermal transfer method, an ink ribbon or sheet in which an ink layer in which a high concentration of transfer dye is dispersed in an appropriate binder resin is applied, and the transferred dye is A transfer medium such as photographic paper coated with a dyeing resin that receives the ink is brought into close contact with a certain pressure, and heat is applied according to the image information from a thermal recording head located on the ink sheet, and the ink sheet is The transfer dye is thermally transferred according to the amount of heat applied to the dye receiving layer.

The above operation is performed by subtracting the three primary colors of subtraction,
The so-called dye diffusion thermal transfer method is characterized by obtaining a full-color image having continuous gradation by repeating each of the image signals separated into yellow, magenta, and cyan. It is attracting attention as an excellent technology for obtaining high-quality images comparable to silver halide color photographs.

[0005] However, this method is a major drawback in that a large amount of waste is generated due to disposable ink sheets and high running costs are hampered.
This is the same in the fusion heat transfer system. As described above, the conventional thermal transfer method has high image quality, but the running cost is high because the dedicated photographic paper and the disposable ink ribbon or sheet are used.

Although the heat-developed silver halide method has high image quality, the running cost and the apparatus cost are also high because dedicated photographic paper and disposable ink ribbons or sheets are used. On the other hand, the ink jet method is described in JP-B-61-599.
No. 11 and Japanese Patent Publication No. 5-217, etc.,
According to image information, electrostatic suction method, continuous vibration generation method (piezo method), thermal method (bubble jet method)
In this method, a small droplet of the recording liquid is caused to fly from a nozzle provided in the recording head and adhere to a recording member, thereby performing recording.

Therefore, there is almost no waste as in the case of using an ink sheet or the like, and the running cost is low. Recently, the thermal method has been widely used because it can easily output a color image. However, in a conventional ink jet, since one droplet of ink forms one pixel, in-pixel gradation is difficult in principle,
High quality image formation is not possible. Attempts have been made to express the pseudo-gradation by the dither method using the high resolution of the ink jet, but the image quality equivalent to that of the sublimation type thermal transfer system cannot be obtained, and the transfer speed has been remarkably reduced.

On the other hand, in the electrophotographic system, the running cost is low and the transfer speed is high, but the apparatus cost is high. As described above, there is no recording method that satisfies all requirements such as image quality, running cost, apparatus cost, and transfer time. Recently, a new recording method that solves these problems has been proposed (Japanese Patent Laid-Open No. 7-89107). That is, the recording liquid is guided to a transfer portion having a porous structure by a capillary phenomenon, and is heated by an appropriate heating means such as a laser beam to vaporize the recording liquid or generate a mist having a diameter of 1 μm or less, This is a non-contact type dye-flying thermal transfer recording system in which image data is transferred onto photographic papers that are arranged opposite to each other with a gap of 10 to 300 μm.

In such a non-contact type thermal transfer recording system, the surface area of the heating section (transfer section) increases due to the above-mentioned porous structure, and the recording liquid is constantly supplied to the recording liquid heating section by capillary action, and is supplied there. In this state, a portion of the recording liquid is evaporated by selectively applying a heat amount according to the recording information by a heating means (for example, a laser beam) in this state, and an electric power generated by a color video camera or the like is obtained. The amount of recording material corresponding to the recording information corresponding to a typical image can be transferred to a non-recording medium by transferring it to a non-recording medium in the form of minute vapors or droplets, and can be transferred onto the recording medium.

Therefore, it is possible to form a large number of droplets having a smaller size than in the known ink jet system, and to freely control the number of droplets to be generated according to the heating energy corresponding to the information recorded in the recording liquid heating section. Since it is possible to perform multi-value density gradation, it can be equivalent to a silver halide image or
It is possible to obtain a recording (for example, a full-color image) having a higher image quality.

Further, since the thermal transfer recording system is used, it has the above-mentioned features such as miniaturization, easy maintenance, quickness, high quality of image, and high gradation. However, it has been found that this thermal transfer recording system has the above-mentioned excellent features and also has a problem to be improved. That is, when the transfer is repeated by this method, charred (decomposed products of the dye and the like) accumulate in the transfer portion, and the so-called kogation, which causes the ejection holes to be clogged, occurs. As a result, the flying state of the recording material fluctuates, and the recording performance tends to deteriorate.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid crystal display having excellent resolution and pixel resolution while simultaneously utilizing the advantages of both the above-described thermal transfer system and the ink-jet system, and at the same time, eliminating those drawbacks, especially the problem of kogation. It is an object of the present invention to provide a thermal transfer recording material that can realize an inner gradation and maintain recording performance for a long time.

[0013]

Means for Solving the Problems The present inventors have found that kogation as described above does not occur due to insufficient heat resistance of a dye used as a recording material, and by using a specific dye, The present inventors have found that the heat resistance of the dye is sufficient, kogation can be greatly reduced, and the life of the head can be prolonged. That is, the present invention is directed to a thermal transfer in which a state is changed to a vaporized state or a droplet state by heating and is transferred to an object to be transferred which is opposed to the transfer part, which is guided by a capillary phenomenon to a transfer part having a porous structure. A thermal transfer recording material comprising a dye represented by the following general formula (I).

Further, the present invention provides a thermal transfer recording system for obtaining a full-color image by repeating thermal transfer of a dye in accordance with an image signal decomposed into three primary colors of a subtractive color mixture of a yellow dye, a magenta dye and a cyan dye. A thermal transfer recording material containing a dye is guided to a transfer portion having a porous structure by a capillary phenomenon, and a state is changed by heating to be transferred to an object to be transferred facing the transfer portion. The present invention relates to a full-color printing method characterized by using a dye represented by the following general formula (I) as a dye. Where "contain"
The term “substantially” refers to the case where the above-mentioned dye occupies a part, and
It also means that it occupies 00% (the same applies to other parts of this specification). General formula (I):

[0015]

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(Wherein ring A represents a heterocyclic ring which may have a substituent, and R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, A group representing an unsubstituted phenyl group, an allyl group or a cycloalkyl group, or a 5- or 6-membered hetero ring together with a nitrogen atom to which R ¹ and R ² are bonded;
R ³ and R ⁴ represent an electron-withdrawing group or a group which forms a ring by bonding with an adjacent carbon atom. )

In the recording material of the present invention, R ¹ and R ² are
The carbon number of the alkyl or alkenyl moiety is 1 to 1
A linear or branched, substituted or unsubstituted alkyl or alkenyl group having 12 carbon atoms,
It is preferably a phenyl group, an allyl group, or a cycloalkyl group having 5 to 10 carbon atoms, which may have an alkyl group or an alkoxy group, a halogen atom, and a fluorine-substituted alkyl group, having up to 8 carbon atoms.

In the recording material of the present invention, R^Three, R^FourIs electronic
When it is a suction group, a cyano group, COOR^FiveGroup, COONR⁶
R⁷Group, COR⁸, CR⁹= C (CN)_TwoGroups
R ^Five, R⁶, R⁷, R⁸Is a hydrogen atom, having 1 to 12 carbon atoms
Alkyl which may be substituted in a linear or branched chain
Alkenyl having 1 to 12 carbon atoms which may be substituted
Or an alkyl group having 1 to 8 carbon atoms as a substituent or
Alkoxy group, halogen atom, fluorine-substituted alkyl group
Optionally having a phenyl group, an allyl group, having 5 to 10 carbon atoms
It is preferably a cycloalkyl group. R⁹Is a hydrogen atom,
An ano group, an alkyl group having 1 to 8 carbon atoms as a substituent or
Is an alkoxy group, a halogen atom, a fluorine-substituted alkyl group
Represents a phenyl group which may have R^ThreeAnd R^FourIs adjacent
Combined with the carbon atom

[0019]

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R ¹⁰ , R ¹¹ , R ¹³ , and R ¹⁴ each represent a group having 1 to 12 carbon atoms which may be substituted in a linear or branched chain. Group, an optionally substituted alkenyl group having 1 to 12 carbon atoms, an alkyl or alkoxy group having 1 to 8 carbon atoms as a substituent, a halogen atom, a phenyl group optionally having a fluorine-substituted alkyl group, an allyl group And a cycloalkyl group having 5 to 10 carbon atoms. R ¹² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may be substituted in a linear or branched chain, an alkoxy group having 1 to 12 carbon atoms which may be substituted in a linear or branched chain. Group, carbon number 1
Straight-chain or branched-chain alkoxycarbonyl group which may be substituted, having 1 to 12 carbon atoms
An alkyl group or an alkoxy group, a halogen atom, a phenyl group which may have a fluorine-substituted alkyl group, or a linear or branched alkylamino group having 1 to 12 carbon atoms, which is represented by R ¹⁵ represents a cyano group or an aminocarbonyl group, and R ¹⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may be substituted. R ¹⁷ represents a carbonyl group, an oxygen atom or a sulfur atom; rings B and C represent an optionally substituted benzene ring; X, Y and Z represent a nitrogen atom or C—R ¹⁸
(Provided that R ¹⁸ is a hydrogen atom, a cyano group, a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted, a linear or branched chain having 1 to 12 carbon atoms) An optionally substituted alkoxy group, a cycloalkyl group having 5 to 10 carbon atoms, an alkyl group or alkoxy group having 1 to 8 carbon atoms as a substituent, a halogen atom, a phenyl group or a phenoxy optionally having a fluorine-substituted alkyl group (Representing a group).

When ring A is a pyridine ring, it may have an alkyl or alkoxy group having 1 to 8 carbon atoms, a halogen atom, or an alkoxycarbonylamino group having 1 to 8 carbon atoms as a substituent. Ring A has the general formula (II) or (III)

[0022]

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A ¹ represents a hydrogen atom, a linear or branched alkyl group which may be substituted, having 1 to 8 carbon atoms, and a substituent having 1 to 8 carbon atoms.
Represents a phenyl group which may have an alkyl group or an alkoxy group, a halogen atom, and a fluorine-substituted alkyl group;
A ² represents a hydrogen atom or a cyano group; A ³ represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may be substituted, and a C 1 to C 8 substituent.
Represents a phenyl group which may have an alkyl group or an alkoxy group, a halogen atom, and a fluorine-substituted alkyl group.

The above substituted alkyl group has 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, as a total number of carbon atoms of the substituted alkyl group.
A hydroxy-substituted alkyl group such as a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 4-hydroxybutyl group; a benzyl group, a p-chlorobenzyl group, and a 2-phenylethyl group 2-methoxyethyl group, 2
An ethoxyethyl group, a 2- (n) propoxyethyl group,
2- (iso) propoxyethyl group, 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group,
2-methoxypropyl group, 4-methoxybutyl group, 3-
Methoxybutyl group, 2,3-dimethoxypropyl group,
An alkoxy-substituted alkyl group such as a 2,2-dimethoxyethyl group; a 2- (2-methoxyethoxy) ethyl group;
(2-ethoxyethoxy) ethyl group, 2- (2- (n)
An alkoxyalkoxy-substituted alkyl group such as a propoxyethoxy) ethyl group, a 2- (2- (n) butoxyethoxy) ethyl group, or a 2- {2- (2-ethylhexyloxy) ethoxy} ethyl group; a 2-phenethyloxyethyl group;
Aralkyloxy-substituted alkyl groups such as 2-benzyloxyethyl group; acyloxy-substituted alkyl groups such as 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-trifluoroacetyloxyethyl group; 2-methoxycarbonylethyl group; An alkoxycarbonyl-substituted alkyl group such as a 2-ethoxycarbonylethyl group; a heterocyclic-substituted alkyl group such as a furfuryl group and a tetrahydrofurfuryl group; an alkenyloxy-substituted alkyl group such as a 2-allyloxyethyl group; a 2-phenoxyethyl group; −
And an aryloxy-substituted alkyl group such as a (p-chlorophenoxy) ethyl group.

The unsubstituted alkyl group is a linear or branched alkyl group having 1 to 12 carbon atoms, specifically, ethyl, i-propyl, n-propyl, n-butyl, i-butyl -Butyl, pentyl, hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-dodecyl and the like. Examples of the alkenyl group include those having the same carbon number as the above-mentioned alkyl group and having at least one double bond.

The substituted alkoxy group preferably has 2 to 8 carbon atoms as a whole of the substituted alkoxy group.
Hydroxy-substituted alkoxy groups such as 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropoxy group and 4-hydroxybutoxy group; phenyl substitution such as benzyloxy group, p-chlorobenzyloxy group and 2-phenylethoxy group Alkoxy group; 2-methoxyethoxy group, 2-ethoxyethoxy group, 2- (n) propoxyethoxy group, 2- (iso) propoxyethoxy group, 3-methoxypropoxy group, 4-methoxybutoxy group, 3-methoxybutoxy group An alkoxy-substituted alkoxy group such as a 2,3-dimethoxypropoxy group or a 2,2-dimethoxyethoxy group; a 2- (2-methoxyethoxy) ethoxy group, a 2- (2-ethoxyethoxy) ethoxy group,
2- (2- (n) propoxyethoxy) ethoxy group, 2
-(2- (n) butoxyethoxy) ethoxy group, 2-
Alkoxyalkoxy-substituted alkoxy groups such as {2- (2-ethylhexyloxy) ethoxy} ethoxy group;
Aralkyloxy-substituted alkoxy groups such as phenethyloxyethoxy group and 2-benzyloxyethoxy group; acyloxy-substituted alkoxy groups such as 2-acetyloxyethoxy group, 2-propionyloxyethoxy group and 2-trifluoroacetyloxyethoxy group; Alkoxycarbonyl-substituted alkoxy groups such as methoxycarbonylethoxy group and 2-ethoxycarbonylethoxy group; heterocyclic-substituted alkoxy groups such as furfuryloxy group and tetrahydrofurfuryloxy group; alkenyloxy-substituted alkoxy groups such as 2-allyloxyethoxy group An aryloxy-substituted alkoxy group such as a 2-phenoxyethoxy group and a 2- (p-chlorophenoxy) ethoxy group.

As the unsubstituted alkoxy group, a linear or branched alkoxy group having 1 to 12 carbon atoms, specifically methoxy, ethoxy, i-propoxy, n-propoxy, n-butoxy, i-butoxy, benzyloxy, hexyloxy, 2-ethylhexyloxy, n-
Groups such as octyloxy, n-decyloxy, n-dodecyloxy and the like can be mentioned. The above cycloalkyl group is a cycloalkyl group having 6 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
Examples thereof include cycloalkyl groups having 5 to 10 carbon atoms which may have about the following substituents.

The above-mentioned substituted phenyl group has 1 carbon atom.
Straight-chain and branched-chain alkyl groups having 1 to 8 carbon atoms;
Linear or branched alkoxy groups; halogen atoms such as fluorine, chlorine, bromine and iodine; and alkyls having 1 to 8 carbon atoms substituted by fluorine such as trifluoromethyl. No. Particularly preferred examples of R ¹ and R ² include a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms; a linear or branched alkoxy group having 1 to 4 carbon atoms, Phenyl group,
1 carbon atom substituted by phenoxy group, allyloxy group, etc.
Linear or branched alkyl group having 1 to 4 carbon atoms; alkyl group having 1 to 10 carbon atoms substituted with a tetrahydrofuryl group; allyl group; cyclohexyl group; phenyl group; Examples thereof include a chain alkyl group, a linear or branched alkoxy group having 1 to 4 carbon atoms, and a phenyl group substituted with a fluorine atom, a chlorine atom, a trifluoromethyl group, or the like.

When R ¹ and R ² are substituted phenyl groups,
The substituents may be in any combination of 1 to 3 substituents. Particularly preferred examples of R ³ and R ⁴ include a cyano group, a COOR ⁵ group, and a CR ⁹ =
(CN) ₂ groups and the like. In this case, as R ⁵ , a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms; a linear or branched alkoxy group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group, A linear or branched alkyl group having 1 to 4 carbon atoms substituted with an allyloxy group; an allyl group; a cyclohexyl group; a phenyl group; a linear or branched alkyl group having 1 to 4 carbon atoms; Examples thereof include a phenyl group substituted with an alkoxy group, a fluorine atom, a chlorine atom, a trifluoromethyl group and the like. R ⁹ includes a hydrogen atom, a cyano group, a phenyl group and the like. When R ³ and R ⁴ represent a group which forms a ring by bonding with an adjacent carbon atom, the following rings are particularly preferred.

[0030]

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(Wherein R ¹² represents a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms; a linear or branched alkoxy alkoxy group having 1 to 8 carbon atoms; a phenyl group) , A linear or branched alkyl group having 1 to 4 carbon atoms substituted with a phenoxy group, an allyloxy group or the like; a linear or branched alkyl group or an alkoxy group having 1 to 4 carbon atoms as a substituent A phenyl group which may have a fluorine atom, a chlorine atom, a trifluoromethyl group or the like; a linear or branched alkylamino group having 1 to 8 carbon atoms which may be substituted. ¹³ and R ^{14 each} represent a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms;
A linear or branched alkyl group having 1 to 4 carbon atoms, which is substituted with a linear or branched alkoxy group, phenyl group, phenoxy group, allyloxy group, or the like; and a tetrahydrofuryl group An alkyl group having 1 to 10 carbon atoms; an allyl group; a cyclohexyl group; a phenyl group; a linear or branched alkyl group having 1 to 4 carbon atoms, and a linear or branched alkoxy group having 1 to 4 carbon atoms. And a phenyl group substituted by a fluorine atom, a chlorine atom, a trifluoromethyl group, or the like. As R ¹⁵ , a cyano group is particularly advantageous. R ¹⁶ is a hydrogen atom, having 1 to 1 carbon atoms.
And 4 linear or branched alkyl groups.

X, Y and Z are each a nitrogen atom or C-
R ¹⁸ groups (where R ¹⁸ is a hydrogen atom, a cyano group, a
8, a linear or branched alkyl group or alkoxy group, a cyclohexyl group, an alkyl or alkoxy group having 1 to 4 carbon atoms as a substituent, a fluorine atom, a chlorine atom, and a trifluoromethyl group. A phenyl group or a phenoxy group). Particularly preferred as ring A are pyridine which may have an alkyl or alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, or an alkoxycarbonylamino group having 1 to 4 carbon atoms as a substituent. A ring or; a compound represented by the general formula (I
Heterocycle selected from I) and (III)

[0033]

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And the like. In this case, A ¹ is a hydrogen atom; a linear or branched alkyl group having 1 to 4 carbon atoms; a linear or branched alkyl group or an alkoxy group having 1 to 4 carbon atoms as a substituent; Examples include a fluorine atom, a chlorine atom, and a phenyl group which may have a trifluoromethyl group. A ² includes a hydrogen atom and a cyano group, and A ³ includes a hydrogen atom; a chlorine atom;
4 straight-chain or branched-chain alkyl groups; having a straight-chain or branched-chain alkyl or alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, or a trifluoromethyl group as a substituent; And a phenyl group. Specific examples of the dye represented by the general formula (I) include those shown in Table 1 below, but the present invention is not limited to these dyes.

[0035]

[Table 1]

[0036]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

The thermal transfer recording material of the present invention is, specifically,
This is a liquid recording material which is vaporized by heating or generates a mist having a diameter of 20 μm or less, and is transferred onto an object to be transferred opposed to each other via a gap of 10 to 300 μm.
By non-contact transfer through such a gap, as described above, both high image quality and immediacy are realized,
It is possible to reduce the weight, transfer to plain paper without generating waste, and perform color recording with low power consumption and low running cost.

The above-mentioned porous structure has a function of holding and supplying the recording material by its capillary action, and particularly has a height of 0.2 to 3 μm on one side or a diameter of 1 to 15 μm. Is good. In this case, a porous structure is formed by arranging three or more rows and three or more columns having a height of one side of 0.2 to 3 μm or a diameter of 1 to 15 μm at intervals of 0.3 to 3 μm. You may.

Such a porous structure (for example, a concavo-convex structure composed of a large number of columns) has the following three remarkable effects. That is, the first effect is that the recording liquid can be spontaneously supplied to the recording portion by the capillary phenomenon due to the large surface area formed by the above-mentioned uneven structure.
The second effect is that the surface tension of the liquid generally decreases as the temperature increases, so that when the recording liquid is heated, the surface tension at the center of heating of the recording liquid is lower than the surface tension at the outer periphery thereof, and the recording liquid at the center part is reduced. However, since the heating portion has the above-described uneven structure, the movement of the recording liquid to the outer peripheral portion can be suppressed, and a decrease in transfer sensitivity can be prevented.

The third effect is that a large number of concave portions in the concave-convex structure of the recording portion each serve as a fine discharge portion, so that the number of very fine recording liquids corresponding to the amount of heat applied to the recording portion is reduced. Droplets are ejected, fly into the space, and are adsorbed on the opposing recording medium such as photographic paper. Using this principle,
The in-pixel gradation that was impossible with the ordinary ink-jet method was enabled.

That is, by providing the above-mentioned porous structure (concavo-convex structure) in the heating section, the surface area increases, and the recording liquid can be constantly supplied to the recording liquid heating section by capillary action and held there. In this state, a heating means (for example, a laser beam) is used to selectively apply heat in accordance with the recording information, thereby evaporating a part of the recording liquid to cause an increase in pressure, and an electric power generated by a color video camera or the like. The recording material in an amount corresponding to the recording information corresponding to the typical image is converted into fine droplets, transferred to the recording medium, and transferred onto the recording medium.

In this case, a large number of droplets having a smaller size can be formed as compared with the known ink jet system, and the number of droplets generated can be freely adjusted according to the heating energy corresponding to the information recorded in the recording liquid heating section. Since control can be performed, multi-value density gradation can be achieved, and recording (for example, a full-color image) having image quality equal to or higher than that of a silver halide image can be obtained. Therefore, by using a head having a special structure capable of thermally transferring very small recording droplets on demand, it is possible to express a density gradation of 128 or more in one pixel per color. Can be realized.

In order to form such a porous structure, for example, a porous alumina having an average particle size of 0.1 to 2 μm is formed by adding 5 to 2 μm.
A method of laminating glass beads having an average particle size of 0.5 to 3 μm to a thickness of 5 to 20 μm, a method of forming a large number of silicon whiskers having an average diameter of 0.5 to 2 μm and a height of 2 to 10 μm to 1 to 3 μm It can also be manufactured by a method such as a method of growing on a substrate at intervals of.

However, in order to precisely control the transfer amount, in particular, a semiconductor processing technique such as RIE (reactive ion etching) or powder beam etching is used to make the size of one side or diameter 0.5 to 3 μm. Height 1-15μ
A structure in which fine columns made of glass or silicon having a size in the range of m are regularly arranged in three or more rows and three or more columns at intervals of 0.5 to 3 μm is preferable. Further, it is preferable to form a porous structure having heat resistance of 300 ° C. or more, and to make the generated droplets fly to a recording medium opposed to the recording liquid heating unit with a gap of 10 to 300 μm.

Although such a porous structure has the above-mentioned excellent action, its small size makes it possible to deteriorate the recording material during recording (particularly, repetitive recording) by heating the recording material, such as decomposition products. Tends to adhere to the porous structure, causing clogging and impairing its action. However, the dye represented by the general formula (I) used in the recording material of the present invention has more than sufficient heat resistance to heating and hardly causes kogation due to decomposition products. Even at times, the action of the porous structure can be maintained and effectively exerted.

When the recording material of the present invention is heated to 300.degree. C. or more, 90% by weight or more is vaporized, and the residue is 10% by weight or less. And a solvent having a boiling point of 150 ° C. or higher to be dissolved or dispersed by 5% by weight or more. The solvent used in this recording liquid is one that sufficiently dissolves or disperses the above-mentioned dye, and has a boiling point of 15
Those having a temperature of 0 ° C. or higher are preferred. This is because the porous structure has a large surface area, the solvent is evaporated or volatilized unless the boiling point is higher than 150 ° C. or higher, and the recording portion dries,
In addition, the recording liquid concentration fluctuates to deteriorate the recording performance.

In particular, the solvent has a melting point of 50 ° C. or less, a boiling point in the range of 150 ° C. to 400 ° C., and is preferably colorless. If the melting point exceeds 50 ° C., the melting point of the dye is generally 100 ° C. or higher. Therefore, the recording liquid prepared by mixing the dye and the solvent solidifies in the range from room temperature, which is the non-transferred recording portion temperature, to 50 ° C. Easier to do.
If the boiling point is lower than 150 ° C., the recording portion is exposed to the atmosphere, so that only the solvent tends to volatilize from the recording liquid. When the boiling point is 400 ° C. or higher, the efficiency of vaporization is low, and the transfer sensitivity tends to decrease.

The solvent preferably has a molecular weight of 450 or less. If the molecular weight is too high, the expansion rate during vaporization is low, and the transfer sensitivity tends to decrease. Further, a solvent having a residual ratio of 0.01% by weight or less when heated to 200 ° C. in air is preferable. The solvent is PPC paper (plain paper),
It is preferable to have the property of being spontaneously absorbed by fibers such as art paper from the viewpoint of transfer to plain paper.

The solvent is 5% by weight of the above dye at 50 ° C. or less.
As described above, especially in order to dissolve 10% by weight or more, the value of the solubility parameter of the solvent at 25 ° C. (as defined by JH Hildebrand) is preferably in the range of 7.5 to 10.5. preferable. Further, it is preferable that the flash point is 150 ° C. or higher, the toxicity to the human body is low, and the color is colorless. When the solubility parameter exceeds 10.5, the solubility of the dye becomes low, and the reproducibility of the transfer sensitivity is liable to deteriorate due to the adsorption of water vapor in the air. When the solubility parameter is less than 7.5, the solubility of the dye tends to be low.

Specifically, di- and trialkyl esters of aromatic carboxylic acids such as phthalic acid and trimellitic acid; succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid Dialkyl esters of aliphatic dicarboxylic acids such as; octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, alkyl esters of aliphatic monocarboxylic acids such as myristic acid; diethylene glycol, triethylene glycol,
Tetraethylene glycol, dipropylene glycol,
Dialkyl ethers of glycols such as tripropylene glycol; ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 2,2,4-trimethyl Monoalkyl ether monoalkyl esters of glycols such as pentanediol; ethylene glycol, propylene glycol,
1,4-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 2,
Dialkyl esters of glycols such as 2,4-trimethyl-pentanediol; aromatic hydrocarbons such as alkylbenzene and alkylnaphthalene;

The alkyl group of the carboxylic acid alkyl ester is substituted with a linear or branched unsubstituted alkyl group or a heterocyclic group such as an alkoxy group, an aryloxy group, an aryl group or a tetrafurfuryl group. An alkyl group having 1 to 20 carbon atoms is suitable. Further, as the alkyl group of the above-mentioned alkyl esters and alkyl ethers of glycols, a linear or branched one having about 1 to 20 carbon atoms is suitable.

Particularly preferred solvents are dibutyl phthalate, dioctyl phthalate, diethyl sebacate, dibutyl sebacate, dioctyl sebacate, di (2-ethylhexyl) sebacate, diethyl azelate,
Dibutyl azelate, dioctyl azelate, di (2-ethylhexyl) azelate, ethyl decanoate, propyl decanoate, butyl decanoate, amyl decanoate, hexyl decanoate, heptyl decanoate, Octyl decanoate, (2-ethylhexyl) decanoate, decyl decanoate, ethyl octanoate, propyl octanoate, butyl octanoate, amyl octanoate, hexyl octanoate, heptyl octanoate, octyl octanoate, octane Acid octyl ester, octanoic acid (2-ethylhexyl) ester, octanoic acid decyl ester, octanoic acid (2-butoxyethyl) ester,
Octanoic acid (2-phenoxyethyl) ester, octanoic acid (2-phenylethyl) ester, octanoic acid tetrahydrofurfuryl ester, dodecanoic acid butyl ester, myristic acid butyl ester, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol di Butyl ether,
Tetraethylene glycol dimethyl ether, diethylene glycol monobutyl ether acetate, 2,2
4-trimethyl-pentanediol diisobutyl ester, acetyl tributyl citrate and the like.

The dyes used in the conventional ink-jet system generally include many acidic dyes, which are hydrophilic and flow on the recording paper when they adhere to the recording paper.
It is poor in water resistance, hardly develops color, and easily generates kogation due to self-decomposition due to heat during recording. On the other hand, since the above-mentioned dye does not cause such a phenomenon, the dye adheres well to the recording paper and develops more than enough color, and kogation hardly occurs.

In addition, when a dialkyl phthalate is used in combination with the dye, the solvent has good permeability into the recording paper, and can sufficiently adhere the dye. It also acts as a color-forming aid for forming a color. Therefore, when this recording liquid is used, PP
Transfer onto C paper is possible, and a high-quality image can be formed. Further, the dye concentration of the recording liquid was conventionally at most 5% by weight, but in the recording liquid composed of the above combination, the solvent amount can be set in a wide range of 50 to 90% by weight, and the dye concentration is 10% by weight. As described above, the image density can be improved.

The transfer head using the recording material of the present invention may comprise a recording section provided with a heating means, an ink tank for storing a recording liquid, and a recording liquid passage connecting the recording section and the ink tank. The entire transfer head can be heated to 50 ° C. in order to adjust the viscosity of the recording liquid. In order to shorten the transfer time, two recording units are provided on one recording head.
More than one can be provided. The recording liquid consumed in the recording unit can be continuously supplied to the recording unit through the recording liquid passage.

The heating means is a heating element such as a resistance heater,
A laser whose output changes in accordance with recording information, a combination of a laser and a laser light absorber (photothermal converter) provided in a recording unit, or the like can be used. When a semiconductor laser is used as a laser, a small and lightweight head can be configured with high controllability. The resistance heater is manufactured by directly attaching a conductive substance such as polysilicon on the recording unit.

The photographic paper which can be used for the transfer of the recording material of the present invention is plain paper such as PPC paper and high quality paper such as art paper. In addition, a special paper prepared by applying polyester, polycarbonate, acetate, epoxy resin, polyvinyl chloride, or the like on a base paper as a resin for coloring a dye can also be used. In order to improve the storage stability of the obtained image, it is effective to laminate a resin film on the photographic paper after transfer.

In order to achieve multicolor recording (especially full color) using the recording material of the present invention, a recording liquid containing a dye exhibiting one of the three primary colors of subtractive color mixing, A recording liquid containing at least one kind of dye exhibiting three subtractive primary colors is selectively heated. For example, this operation is decomposed into yellow (Y), magenta (M), and cyan (C). Full colorization can be achieved by repeating each of these image signals.

With the demand for high performance of printing technology in recent years, it is required to carefully select the color tone of each of Y, M, and C in full-color printing.
It is also excellent in that a beautiful color tone satisfying the demand can be obtained. The dye of the present invention is preferable because a beautiful color tone can be obtained particularly when transferred to recording paper coated with a base paper with a polyester resin.

[0063]

The present invention will be described below in more detail with reference to examples. First, a description will be given with reference to the drawings. 1 to 4 are views showing a vaporized thermal transfer printer head used in the embodiment. FIG. 1 (a) is a sectional view thereof, FIG. 1 (b) is a perspective view, FIG. 2 is a plan view, and FIG. FIG. 4 is a plan view showing a state in which a cover 7 described later is removed, and FIG. 4 is a partially enlarged view of a part thereof. FIG. 5 is a schematic diagram of a serial type printer. Figure 1
As shown in FIG. 3, the printer head 1 includes an aluminum head base 2 also serving as a heat sink, a vaporizing section heated by a heater according to image information, and a recording liquid for guiding the recording liquid to the vaporizing section by a capillary action. A heater chip 3 integrally formed on a silicon substrate and a driver IC 5 covered with a potting resin 4 are mounted, and wiring is formed so as to supply current to each heater in accordance with image data to be transferred. Printed circuit board 6 and driver I
It is composed of a cover 7 which also serves as protection of C5 and a supply path of the dye.

Here, a recording liquid introduction hole 8 for introducing a recording liquid into the printer head 1 is provided in the head base 2.
When the heater chip 3 is adhered to the head base 2, a groove 9 is formed as an escape area for an excess adhesive that protrudes.
The inside of the cover 7 is a recording liquid supply path 10 for supplying the recording liquid to the recording liquid introduction path of the heater chip 3. In addition, the printed circuit board 6 includes a connector terminal 11.
Is provided. The surface of the heater chip 3 is covered with a Ni sheet 3a for protection, and a sheet resist 3b for forming a recording liquid introduction path is formed in a line inside the Ni sheet 3a.

The heater chip 3 has a plurality of heaters for heating and vaporizing the recording liquid, wiring for applying a signal voltage based on an image signal to each of the heaters, and energizing the recording liquid. The recording liquid introduction path for supplying the liquid is formed by a lithography process.

That is, as shown in FIG. 4 (enlarged view of the vaporizing portion 13 at the tip of the heater chip 3 and the vicinity thereof), for example, when the pitch Lp = 84.7 μm, the heater 14 has a total of 2
56 are formed. At this time, one heater 14 is 1
Since the dots are transferred, a resolution of 300 DPI can be realized. Each of the heaters 14 is formed of polysilicon having a size of 20 μm × 20 μm. The heater 14 is connected to an individual electrode 15 made of aluminum and a common electrode 16 for applying and energizing a signal voltage based on an image signal. Have been. Here, the vaporizing sections 13 are separated from each other by the partition walls 17, and the recording liquid is stored in the concave portion (the recording liquid storing section 18) surrounded by the partition walls 17. On the heater 14 and around it, a fine columnar small column 19 having a diameter of 2 μm, a partition of 2 μm, and a height of 6 μm is formed of 13 × 13 via a protective film SiO ₂ (not shown). A group of books is provided as one of the constituent elements of the vaporizing unit 13.

The height of the small column 19 is determined by the recording liquid storage section 1.
8, that is, the height from the bottom surface to the top surface thereof, that is, the height of the partition wall 17 surrounding the recording liquid storage portion 18 of each heater 14, Are provided with a minute gap from each other so as to have a porous structure. Accordingly, the porous structure causes a capillary action, and thus each of the small columns 19 can hold the recording liquid in the recording liquid storage portion 18. At the same time, heater 1
When the recording liquid is heated in step 4, the surface tension of the recording liquid decreases as the temperature rises, but the recording liquid can be prevented from escaping from the vicinity of the surface of the heater 14 by the capillary action. Therefore, at the time of image transfer, a necessary recording liquid is continuously supplied.

As shown in FIG. 1A, the printer head 1 comes into contact with the recording material (printing paper) 12 at only one end 2a of the base and has a predetermined angle with respect to the recording material 12. So it is held. Thus, the distance between the vaporizing section 13 and the recording material 12 can be kept constant. For example, the center position of the heater 14 of the vaporizing section 13 (FIG. 1)
The dashed line in (a)) is located 1.85 mm from the head base end 2 a in contact with the recording material 12, and the heater is formed on a 0.4 mm thick silicon substrate. The angle between the head base 2 and the recording material 12 such that the distance between the recording material 12 and the recording material 12 is 50 μm (however, the thickness of the adhesive layer between the silicon substrate and the head base 2 is 10 μm). At 14 °.

As described above, by appropriately changing the distance from the head base end 2a to the center position of the heater and the angle between the recording material 12 and the head base 2, the heater 14 and the recording material 12 Can be set to an arbitrary size. In this embodiment, a serial type printer as shown in FIG. 5 having the above-described printer heads 1Y, 1M and 1C for each color of yellow (Y), magenta (M) and cyan (C) was used. . Each printer head is connected to a head drive circuit board (not shown) via a flexible harness.

This serial type printer has a vertical (X
A paper feed roller 20 for transporting paper in the direction
A head feed shaft 21 for scanning the printer head in a direction (Y direction) orthogonal to the X direction is provided. The head feed shaft 21 is freely rotated by a motor (not shown) based on image information, and the printer head 1 is moved. It can be scanned. The paper feed in the vertical direction and the head scan in the horizontal direction are configured to be performed alternately.

Since each of the printer heads 1Y, 1M and 1C is provided with 256 heaters 14, the serial type printer used in this embodiment is
It has the ability to print 256 lines in one scan. In addition, at the end of one scan, the platen 2 is moved by the paper feed roller 20 also serving as a head support.
The recording material (printing paper) 12 on the sheet 2 is fed by 256 lines,
Since it is possible to start printing by sequentially changing the timing for each color so that the heads 1Y, 1M, and 1C of each color start printing from a predetermined position on the printing paper 12, a color image can be printed by one scan. You can do it. FIG.
Instead of the serial type printer shown in FIG. 1, a color printer having a head configured in a line type can be used. Hereinafter, an example of recording used in the above-described serial type printer will be specifically described.

Example 1 No. 1 in Table-1 4% by weight of 1 dye in dibutyl phthalic acid
To obtain a magenta recording solution.
When this was introduced into the ink tank from the recording liquid introduction hole of the printer head shown in FIG. 1, the recording liquid spontaneously was introduced into the vaporizing portion at the tip of the recording heater chip through the passage. Next, by applying the following pulse voltage to the heater of the printer head, the recording liquid was thermally transferred to photographic paper.

(Pulse voltage conditions) 80 mW, one gradation, ON time 12 μs, OFF time 2 μs, 1 pulse, 256 pulses applied per dot. As a result of thermal transfer under the above conditions, magenta dots having an optical density of 0.61 could be formed on A6 plain paper as measured by a Macbeth reflection densitometer. When this transfer was continued, scorching occurred on the columnar portion of the printer head, and the transfer of magenta color became impossible, but a large number of prints of 5,000 sheets could be performed.

Example 2 Nos. 1 and 2 in Table 1 were used as dyes. The same test as in Example 1 was carried out except that the dye No. 1 was used and a magenta recording solution dissolved in diethylene glycol dibutyl ether at a concentration of 5% by weight was used, and a magenta dot having an optical density of 1.07 was obtained. Could be formed on plain paper of A6, and when this transfer was continued, 5000 prints could be made.

[0075]

According to the recording material of the present invention, the dye used has more than sufficient heat resistance to heating, and kogation due to decomposition products hardly occurs. The characteristics of the structure can be stabilized and can be exhibited effectively. In this case, a large number of small-sized droplets can be formed by the porous structure, and the number of generated droplets can be freely controlled according to the heating energy corresponding to the information recorded in the recording liquid heating section. A value density gradation becomes possible, and a recording (for example, a full-color image) having an image quality equal to or higher than that of a silver halide image can be obtained. In addition, since recording is performed by the thermal transfer method, the size of the apparatus can be reduced, and maintainability, immediacy, high-quality images,
It has features such as high gradation.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view (FIG. 1A) and a lower perspective view (FIG. 1B) of a printer head used in an embodiment.

FIG. 2 is a plan view of a printer head used in the embodiment.

FIG. 3 is a plan view of a printer head used in the embodiment.

FIG. 4 is a partially enlarged view of a printer head used in the embodiment.

FIG. 5 is a schematic view of a serial type printer used in the embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Printer head 2 Head base 3 Heater chip 4 Potting resin 5 Driver IC 6 Printed circuit board 7 Cover 8 Recording liquid introduction hole 9 Groove 10 Recording liquid supply path 11 Connector terminal 12 Recording material (printing paper) 13 Vaporization part 14 Heater 15 Individual electrode 16 Common electrode 17 Partition wall 18 Recording liquid storage unit 19 Column

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/02 B41M 5/26 101Z (72) Inventor Miori Ishida 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi F-term (reference) in Yokohama R & D Co., Ltd. BC02 BC03 BC05 BC12 BC13 BC15 BC16 BC17 BC20 BC32 BC33 BC36 BC49 BC50 BC51 BC52 BC53 BC55 BC65 BC74 BE02 BE12 EA15 EA16 EA17 EA48 GA06

Claims (13)

[Claims] 1. A thermal transfer recording material which is guided by a capillary phenomenon to a transfer portion having a porous structure, changes its state by heating, and is transferred to an object to be transferred facing the transfer portion. A thermal transfer recording material containing the dye represented by I). Embedded image (In the formula, ring A represents a heterocyclic ring which may have a substituent,
R ^1, R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group, or an allyl group or a cycloalkyl group, R ^1, R ² is a bond R ³ and R ⁴ represent an electron-withdrawing group or a group which forms a ring by bonding with an adjacent carbon atom together with a nitrogen atom which forms a 5- or 6-membered hetero ring. Represent. ) 2. In the formula (I), R ³ and R ⁴ are each a cyano group, a COOR ⁵ group, a CONR ⁶ R ⁷ group, a COR ⁸ group,
The electron-withdrawing group selected from CR ⁹ ＣC (CN) ₂ groups, or a group in which R ³ and R ⁴ are bonded together with an adjacent carbon atom to form a heterocyclic ring selected from the following formula: Thermal transfer recording material. Embedded image (Provided that R ⁵ , R ⁶ , R ⁷ and R ⁸ are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group,
R ⁹ represents a hydrogen atom, a cyano group, or an optionally substituted phenyl group; R ¹⁰ represents an optionally substituted alkenyl group, an allyl group, or a cycloalkyl group; R ¹⁰ , R ¹¹ , R ¹³ ,
R ¹⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, an optionally substituted alkenyl group, an allyl group, or a cycloalkyl group;
¹² is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted phenyl group, an optionally substituted alkylamino group,
Represents an optionally substituted alkoxycarbonyl group,
R ¹⁵ represents a cyano group, aminocarbonyl group, R ¹⁶ represents a hydrogen atom, an alkyl group which may be substituted, R ¹⁷
Represents a carbonyl group, an oxygen atom or a sulfur atom, rings B and C represent a benzene ring which may have a substituent,
X, Y and Z represent a nitrogen atom or a C—R ¹⁸ group (R ¹⁸
Represents a hydrogen atom, a cyano group, an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an amino group, an aralkyl group, or an aryloxy group. ) The ring A in the general formula (I) is a pyridine ring and the following general formulas (II) and (III): (Wherein A ¹ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl group,
A ² represents a hydrogen atom, an optionally substituted alkyl group, a halogen atom, an alkylcarbonyl group, an alkoxycarbonyl group, a cyano group, and A ³ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, The thermal transfer recording material according to claim 1, wherein the heterocyclic ring is represented by the following formula: 4. A compound of the formula (I) wherein R ¹ and R ² are a substituted or unsubstituted alkyl group, alkenyl group, allyl group, cyclohexyl group having 1 to 12 carbon atoms and 1 to 8 carbon atoms.
Or a phenyl group which may be substituted with a halogen atom, or a morpholine ring, a piperazine ring, a thiol group together with a nitrogen atom to which R ¹ and R ² are bonded. 2. The thermal transfer recording material according to claim 1, which is a group forming a morpholine ring. 5. Evaporation by heating or having a diameter of 20
The thermal transfer recording material according to any one of claims 1 to 4, wherein the thermal transfer recording material is a recording material that generates a mist of less than or equal to μm and is transferred onto an object to be transferred that is opposed to the object with a gap of 10 to 1000 μm. 6. One side or diameter of 0.5 to 3 μm, 1 to 1
0.5 to 10 μm fine columnar bodies having a height of 5 μm
The thermal transfer recording material according to any one of claims 1 to 5, wherein a porous structure is formed by arranging at least three rows and at least three columns at an interval of. 7. A polymer having a molecular weight of 450 or less and a melting point of 50
C. or lower, a boiling point of 150 ° C. or higher and 400 ° C. or lower, a colorless solvent having a residual ratio of 0.01% by weight or less when heated to 200 ° C. in the air. 7. The thermal transfer recording material according to claim 1, wherein the dye represented by (I) is dissolved in an amount of 3% by weight or more at 50 ° C. or less. 8. The thermal transfer recording material according to claim 1, wherein the solvent is at least one selected from aromatic carboxylic esters, aliphatic carboxylic esters, glycol ethers, glycol esters and aromatic hydrocarbons. 9. The thermal transfer recording material according to claim 8, wherein the aromatic carboxylic acid ester is a dialkyl phthalate. 10. The aliphatic carboxylic acid ester may be a dialkyl succinate, a dialkyl glutarate, a dialkyl adipate, a dialkyl suberic acid, a dialkyl azelate, a dialkyl sebacate, a dialkyl dodecandioic acid, or octane. Acid alkyl ester, nonanoic acid alkyl ester, decanoic acid alkyl ester, dodecanoic acid alkyl ester or myristic acid alkyl ester (provided that the alkyl group of the alkyl ester is substituted with an alkoxy group, an aryloxy group, an aryl group or a heterocyclic group) 9. The thermal transfer recording material according to claim 8, wherein: 11. The glycol ester is ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol,
Tetraethylene glycol, dipropylene glycol,
9. The thermal transfer recording material according to claim 8, which is a monoalkyl ether monoalkyl ester or dialkyl ester of tripropylene glycol or 2,2,4-trimethyl-1,3-pentanediol. 12. The thermal transfer recording material according to claim 8, wherein the glycol ether is diethylene glycol dialkyl ether, triethylene glycol dialkyl ether or tetraethylene glycol dialkyl ether, dipropylene glycol dialkyl ether or tripropylene glycol dialkyl ether. 13. A thermal transfer recording method for obtaining a full-color image by repeating thermal transfer of a dye corresponding to an image signal decomposed into three subtractive primary colors of a yellow dye, a magenta dye, and a cyan dye. A thermal transfer recording method is used, in which a thermal transfer recording material is guided to a transfer portion having a porous structure by a capillary phenomenon, and changes its state by heating and is transferred to an object to be transferred facing the transfer portion. A full-color printing method using a dye represented by the formula (I). Embedded image (In the formula, ring A represents a heterocyclic ring which may have a substituent,
R ^1, R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group, or an allyl group or a cycloalkyl group, R ^1, R ² is a bond R ³ and R ⁴ represent an electron-withdrawing group or a group which forms a ring by bonding with an adjacent carbon atom together with a nitrogen atom which forms a 5- or 6-membered hetero ring. Represent. )