JP2001191648A - 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 an aromatic or 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 salt method has high image quality, the running cost is high and the apparatus cost is high because the dedicated photographic paper and the disposable ink ribbon or sheet are used.

On the other hand, the ink jet system is described in
As described in JP-A-59911 and JP-B-5-217, recording is performed by a method such as an electrostatic suction method, a continuous vibration generation method (piezo method), or a thermal method (bubble jet method) according to image information. The recording is performed by causing a small droplet of the liquid to fly from a nozzle provided in the recording head and to adhere to a recording member. 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 the conventional ink jet, since one droplet of ink forms one pixel, gradation in a pixel is difficult in principle, and a high quality image cannot be formed. 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, the electrophotographic method has a low running cost,
The transfer speed is high, but the equipment cost is high.

As described above, image quality, running cost,
There is no recording method that satisfies all requirements such as 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 occurs due to insufficient heat resistance of a dye used as a recording material, and by using a specific dye, The 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. The present invention relates to 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 the state is changed by heating, and a thermal transfer recording method is used in which the material is 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. Here, “contained” means not only that the above-mentioned dye occupies a part but also substantially 10%.
It also means that it occupies 0% (the same applies to other parts of this specification). General formula (I):

[0015]

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(In the formula, ring A represents an aromatic ring or a hetero ring which may have a substituent, and R ¹ and R ² are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. Represents a substituted or unsubstituted phenyl group, an allyl group, or a cycloalkyl group, or represents a group which forms a 5- or 6-membered hetero ring by bonding to a ring A together with an adjacent nitrogen atom, R ¹ , R ² Is a group that forms a 5- or 6-membered hetero ring together with the nitrogen atom to which it is bonded, and R ³ and R ⁴ represent an electron-withdrawing group or form a ring by bonding with an adjacent carbon atom Represents a group.)

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, when R ³ and R ⁴ are electron-withdrawing groups, cyano groups, COOR ⁵ groups, COON groups
R ⁶ R ⁷ , COR ⁸ , CR ⁹ ＣC (CN) _2, etc., wherein R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom, a carbon atom of 1 to 1;
2, a linear or branched alkyl group which may be substituted, an alkenyl group having 1 to 12 carbon atoms which may be substituted, an alkyl group or an alkoxy group having 1 to 8 carbon atoms as a substituent, halogen Atom, phenyl group which may have a fluorine-substituted alkyl group, allyl group, having 5 to 1 carbon atoms
It is preferably 0 cycloalkyl group. R ⁹ represents a hydrogen atom, a cyano group, an alkyl or alkoxy group having 1 to 8 carbon atoms as a substituent, a halogen atom, or a phenyl group which may have a fluorine-substituted alkyl group. R ³ and R ⁴ are bonded together with adjacent carbon atoms

[0019]

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When a heterocyclic ring selected from the group consisting of R ¹⁰ ,
R ¹¹ , R ¹³ and R ^{14 each} represent a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted;
To 12 optionally substituted alkenyl groups, alkyl or alkoxy groups having 1 to 8 carbon atoms as substituents,
It is preferably a halogen atom, a phenyl group which may have a fluorine-substituted alkyl group, an allyl group, or 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. A linear or branched alkoxycarbonyl group having 1 to 12 carbon atoms, which may be substituted, an alkyl or alkoxy group having 1 to 8 carbon atoms as a substituent, a halogen atom, and a fluorine-substituted alkyl group. Represents an optionally substituted phenyl group, a linear or branched alkylamino group having 1 to 12 carbon atoms, R ¹⁵ represents a cyano group or an aminocarbonyl group, and R ¹⁶ represents a hydrogen atom Represents a linear or branched alkyl group which may be substituted and has 1 to 8 carbon atoms.
R ¹⁷ represents a carbonyl group, an oxygen atom or a sulfur atom, and the rings B and C are an alkyl or alkoxy group having 1 to 8 carbon atoms which may be substituted as a substituent, a halogen atom, a substitution having 1 to 8 carbon atoms. An optionally substituted alkoxycarbonylamino group, an optionally substituted aryloxycarbonylamino group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms
Represents a benzene ring which may have a cycloalkyl group which may be substituted, wherein X, Y and Z are a nitrogen atom or C—R ²³ (where R ²³ is a hydrogen atom, a cyano group, A linear or branched alkyl group which may be substituted with 1 to 12 carbon atoms, an alkoxy group which may be substituted with a linear or branched chain having 1 to 12 carbon atoms, 5 to 5 carbon atoms
And a phenyl or phenoxy group which may have an alkyl or alkoxy group having 1 to 8 carbon atoms as a substituent, a halogen atom, or a fluorine-substituted alkyl group. R ¹⁸ represents an oxygen atom or a C (CN) ₂ group, and R ¹⁹ , R ²⁰ , R ²¹ , R
²² is a hydrogen atom, an alkyl group which may be substituted in a linear or branched chain having 1 to 12 carbon atoms, a halogen atom,
An alkylcarbonylamino group or an alkoxycarbonylamino group which may be substituted in a linear or branched chain having 1 to 12 carbon atoms, an arylcarbonylamino group or an aryloxycarbonylamino group which may be substituted, Represents a cycloalkylcarbonylamino group of 10 to 10, and R ²¹ and R ²² may be a group which forms a 5- or 6-membered ring by bonding. When Ring A is a benzene ring, a naphthalene ring, or a pyridine ring, it may have a C1-8 alkyl or alkoxy group, a halogen atom, or a C1-8 alkoxycarbonylamino group as a substituent. Ring A is represented by the general formula (II) or (II
I)

[0021]

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A ¹ represents a hydrogen atom, a linear or branched alkyl group which may be substituted and has 1 to 8 carbon atoms, and A ¹ has 1 to 8 carbon atoms as a substituent.
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 the 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 an 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; (P
And aryloxy-substituted alkyl groups such as -chlorophenoxy) ethyl group.

As the unsubstituted alkyl group, 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 may have 2 to 25 carbon atoms, more preferably 2 to 25 carbon atoms, as the total number of carbon atoms of the substituted alkoxy group.
20, preferably a 2-hydroxyethoxy group, 2-
Hydroxy-substituted alkoxy groups such as hydroxypropoxy group, 3-hydroxypropoxy group and 4-hydroxybutoxy group; phenyl-substituted alkoxy groups such as benzyloxy group, p-chlorobenzyloxy group and 2-phenylethoxy group; 2-methoxyethoxy group , 2-ethoxyethoxy group, 2- (n) propoxyethoxy group, 2- (is
o) alkoxy-substituted alkoxy groups such as propoxyethoxy group, 3-methoxypropoxy group, 4-methoxybutoxy group, 3-methoxybutoxy group, 2,3-dimethoxypropoxy group, 2,2-dimethoxyethoxy group;
(2-methoxyethoxy) ethoxy group, 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 2-phenethyloxyethoxy group and 2-benzyloxyethoxy group; 2-acetyloxyethoxy group;
Acyloxy-substituted alkoxy groups such as 2-propionyloxyethoxy group and 2-trifluoroacetyloxyethoxy group; alkoxycarbonyl-substituted alkoxy groups such as 2-methoxycarbonylethoxy group and 2-ethoxycarbonylethoxy group; furfuryloxy group and tetrahydrofur A heterocyclic substituted alkoxy group such as a furyloxy group; 2-
Alkenyloxy-substituted alkoxy groups such as allyloxyethoxy group; and aryloxy-substituted alkoxy groups such as 2-phenoxyethoxy group.

The unsubstituted alkoxy group is a linear or branched alkoxy group having 1 to 12 carbon atoms, specifically methoxy, ethoxy, i-propoxy, n-
Propoxy, n-butoxy, i-butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, n
-Octyloxy, n-decyloxy, n-dodecyloxy and the like.

Examples of the cycloalkyl group include a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent having about 6 or less carbon atoms, such as a cyclopentyl group and a cyclohexyl group. Examples of the substituted phenyl group include linear and branched alkyl groups having 1 to 8 carbon atoms; linear and branched alkoxy groups having 1 to 8 carbon atoms; a fluorine atom, a chlorine atom, a bromine atom, A halogen atom such as an iodine atom; and an alkyl group having 1 to 8 carbon atoms substituted by a fluorine atom such as a trifluoromethyl group.

Particularly preferred as R ¹ and R ² are a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms; a linear or branched chain having 1 to 4 carbon atoms. C1-C4 linear or branched alkyl group substituted by alkoxy group, phenyl group, phenoxy group, allyloxy group, etc .; C1-C10 alkyl group substituted by tetrahydrofuryl group; Allyl Group; cyclohexyl group; phenyl group; linear or branched alkyl group having 1 to 4 carbon atoms, linear or branched alkoxy group having 1 to 4 carbon atoms, fluorine atom, chlorine atom, trifluoro group Examples include a phenyl group substituted with a methyl group and 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 together with an adjacent carbon atom, particularly preferred are:

[0030]

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And a ring selected from the group consisting of R¹²age
Linear or branched alkyl having 1 to 8 carbon atoms
Group or alkoxy group; linear or branched having 1 to 8 carbon atoms
Branched alkoxyalkoxy group; phenyl group, pheno
C1-C4 substituted with an xy group, an allyloxy group, etc.
Linear or branched alkyl group; carbon as a substituent
A linear or branched alkyl group having a prime number of 1 to 4, or
Alkoxy group, fluorine atom, chlorine atom, trifluoromethyl
A phenyl group which may have a tyl group or the like;
Linear or branched alkyl which may be substituted
And a killamino group. R¹³, R¹⁴As the carbon
A linear or branched alkyl group of the formulas 1 to 8 or
Alkenyl group; linear or branched having 1 to 4 carbon atoms
Alkoxy group, phenyl group, phenoxy group, allyloxy
C 1-4 straight-chain or branched substituted with a group or the like
Chain alkyl group; substituted with tetrahydrofuryl group
Alkyl group having 5 to 10 carbon atoms; allyl group; cyclohexyl
Phenyl group; linear or branched having 1 to 4 carbon atoms
Chain alkyl group, linear or branched having 1 to 4 carbon atoms
Chain alkoxy group, fluorine atom, chlorine atom, trifur
A phenyl group substituted with an olomethyl group and the like.
You. R^FifteenA cyano group is particularly advantageous. R ¹⁶age
Represents a hydrogen atom, a linear or branched chain having 1 to 4 carbon atoms
Alkyl group.

X, Y and Z are each a nitrogen atom or C-
R ²³ groups (where R ²³ 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).

R ¹⁸ is an oxygen atom or C (CN)
_2, and examples R ¹⁹ is a linear or branched chain optionally substituted by an alkyl group having 1 to 8 carbon atoms, alkylcarbonylamino group, an alkoxycarbonylamino group, a cycloalkyl carbonyl amino group, substituted And a phenoxycarbonylamino group and a phenoxycarbonylamino group. R ²⁰ is a hydrogen atom,
A linear or branched alkyl group having 1 to 8 carbon atoms,
R ²¹ and R ²² include a hydrogen atom, a fluorine atom, a chlorine atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and the like. R ²¹ , R ²²
May be a group bonded to form a benzene ring or a pyridine ring. Particularly preferred as ring A are a benzene ring which may have, as a substituent, an alkyl or alkoxy group having 1 to 4 carbon atoms, a fluorine atom, a chlorine atom, and an alkoxycarbonylamino group having 1 to 4 carbon atoms. , Naphthalene ring or pyridine ring; general formulas (II) and (III)
Heterocycle selected from

[0034]

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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.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

Specifically, the thermal transfer recording material of the present invention comprises
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 act 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 is increased, 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 small 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, using a head having a special structure capable of thermally transferring very small recording droplets on demand, at least 128 or more density gradations within one pixel per color. An ink jet system capable of expressing can be realized. To form such a porous structure, for example, a method of laminating porous alumina having an average particle size of 0.1 to 2 μm to a thickness of 5 to 20 μm, an average particle size of 0.5 to
A method of laminating 3 μm glass beads to a thickness of 5 to 20 μm, a method of growing a large number of silicon whiskers having an average diameter of 0.5 to 2 μm and a height of 2 to 10 μm on a substrate at an interval of 1 to 3 μm, and the like. Can be manufactured.

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 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, a porous structure having a heat resistance of 300 ° C. or more is formed, and the generated droplets are supplied to
It is preferable to fly the recording medium opposed to the recording medium with a gap of 300 μm. Such a porous structure has the above-mentioned excellent function. However, since its size is very small, deterioration caused by heating of the recording material during recording (particularly, repetitive recording), for example, decomposition It tends to adhere to the structure and cause clogging and impair its action.

However, the dye represented by the general formula (I) used in the recording material of the present invention has a sufficient heat resistance to heating and hardly causes kogation due to decomposition products. Even when recording is repeated, the function of the porous structure can be maintained and effectively exerted. When the recording material of the present invention is heated to 300 ° C. or more, 90% by weight or more is vaporized and the residue is 10% by weight or less, and the dye (dye) is 5% at 50 ° C. or less. % Or more of a solvent having a boiling point of 150 ° C. or higher to be dissolved or dispersed.

The solvent used in this recording liquid should be one that sufficiently dissolves or disperses the above-mentioned dye and has a boiling point of 150 ° C. or higher. This is because the above-mentioned porous structure has a large surface area, and if the boiling point is not higher than 150 ° C., the solvent evaporates or volatilizes to dry the recording portion, and the recording liquid concentration fluctuates, and the recording performance changes. Is to deteriorate.

Particularly, 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. When 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 part 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 molecular weight of the solvent is preferably 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 contain many acid 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 the dye can be sufficiently adhered. 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 transferring the recording material of the present invention is plain paper such as PPC paper, high-quality paper such as art paper, etc. In order to obtain a high quality image having particularly high gradation and density. 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 multi-color recording (particularly 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 the printing technology in recent years, in full-color printing, it is required to carefully select the color tone of each of Y, M, and C.
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.

[0068]

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 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 (a partial enlarged view of the vaporizing portion 13 at the tip of the heater chip 3 and its vicinity), for example, the pitch Lp
= 84.7 μm, 256 heaters 14 are formed in total. At this time, since one heater 14 transfers one dot, 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. In addition, a diameter of the heater 14 is 2 mm on and around the heater 14 via a protective film of SiO ₂ (not shown).
A small columnar body 19 having a column diameter of 2 μm, a partition wall of 2 μm, and a height of 6 μm is provided as one of the constituent elements of the vaporizing section 13 in a group of 13 × 13.

The height of the small column 19 is determined by the recording liquid container 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 (the dashed line in FIG. 1A) is set to be 1.85 mm from the head base end 2a in contact with the recording material 12. The distance between the heater 14 formed on a silicon substrate having a thickness of 0.4 mm and the recording material 12 is 5 mm.
The angle between the head base 2 and the recording material 12 is maintained at 14 ° so that the thickness of the adhesive layer between the silicon substrate and the head base 2 is 10 μm.

As described above, by appropriately changing the distance from the head base end portion 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.

Here, since 256 heaters 14 are provided in each of the printer heads 1Y, 1M and 1C, 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 5% by weight of 5 dyes in dibutylphthalic 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 condition) 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 1.03 could be formed on A6 plain paper as measured with 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 could not be performed. However, a large number of prints of 4000 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 yellow recording solution dissolved in dibutyl phthalic acid at a concentration of 10% by weight was used, and a yellow dot having an optical density of 0.77 was obtained. Is A6
The transfer was continued, and 2,000 prints could be made.

Example 3 Nos. 1 and 2 in Table 1 were used as dyes. The same test as in Example 1 was performed except that the dye No. 4 was used and a magenta color recording solution dissolved in dibutyl phthalic acid at a concentration of 10% by weight was used. As a result, a magenta dot having an optical density of 1.17 was obtained. Is A6
Was formed on plain paper, and when this transfer was continued, 3000 prints could be made.

Example 4 Nos. 1 and 2 in Table 1 were used as dyes. The same test as in Example 1 was performed except that a cyan recording solution dissolved in dibutyl phthalic acid at a concentration of 10% by weight using 14 dyes was used. A cyan dot having an optical density of 0.72 was obtained. Could be formed on A6 plain paper, and 2,000 prints could be made when this transfer was continued.

Example 5 As a dye, No. 1 in Table 1 was used. The same test as in Example 1 was carried out except that the dye No. 21 was used and a cyan recording solution dissolved in dibutyl phthalic acid at a concentration of 5% by weight was used, and a cyan dot having an optical density of 0.74 was obtained. Could be formed on A6 plain paper, and 3,000 prints could be made when this transfer was continued.

Example 6 Nos. In Table 1 were used as dyes. The same test as in Example 1 was carried out except that the dye No. 9 was used and a magenta recording solution dissolved in dibutyl phthalic acid at a concentration of 5% by weight was used, and a magenta dot having an optical density of 0.63 was obtained. Was able to be formed on A6 plain paper, and when this transfer was continued, 4000 prints could be made.

Example 7 As dyes, No. 1 in Table 1 was used. The same test as in Example 1 was carried out except that the dye of No. 23 was used and a cyan recording solution dissolved in dibutyl phthalic acid at a concentration of 4% by weight was used, and a cyan dot having an optical density of 0.58 was obtained. Could be formed on A6 plain paper, and 2,000 prints could be made when this transfer was continued.

Example 8 Nos. In Table 1 were used as dyes. The same test as in Example 1 was carried out except that the dye No. 5 was used and a magenta color recording solution dissolved in diethylene glycol dibutyl ether at a concentration of 10% by weight was used. As a result, a magenta dot having an optical density of 1.82 was obtained. Could be formed on plain paper of A6, and when this transfer was continued, 5000 prints could be made.

Example 9 As a dye, No. 1 in Table 1 was used. The same test as in Example 1 was carried out, except that the dye No. 1 was used and a yellow recording liquid dissolved in diethylene glycol dibutyl ether at a concentration of 10% by weight was used, and a yellow dot having an optical density of 1.00 was obtained. Could be formed on A6 plain paper, and this transfer was continued, and 3000 prints could be made.

[0087]

According to the recording material of the present invention, the dye represented by the above general formula (I) has a sufficient heat resistance to heating, and almost no kogation due to decomposition products is obtained. Since it does not occur, the characteristics of the porous structure can be stably maintained even during repeated recording and can be effectively exerted. 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. Further, since the recording is performed by the thermal transfer method, the apparatus can be reduced in size, and has features such as easy maintenance, quickness, high quality of an image, and 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 code FI Theme coat ゛ (Reference) C09B 57/00 B41M 5/26 S C09D 11/02 101Z (72) Inventor Miori Ishida Aoba-ku, Yokohama-shi, Kanagawa 1000 Kamoshitacho Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 2H086 BA02 BA03 BA54 BA56 BA60 BA62 2H111 AA01 AA08 AA12 AA31 AA32 AA48 AB00 BA38 BA39 BA47 BA48 BA49 BA55 BA61 BA71 BA74 BA76 HA12 HA24 HA35 4J039 BC02 BC12 BC12 BC12 BC15 BC16 BC17 BC20 BC32 BC33 BC36 BC44 BC49 BC51 BC52 BC55 BC65 BC74 BE02 BE12 EA15 EA16 EA17 EA48 FA02 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 comprising the dye represented by I). Embedded image (In the formula, ring A represents an aromatic ring or a hetero ring which may have a substituent, and R ¹ and R ^{2 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, It may represent an unsubstituted phenyl group, an allyl group or a cycloalkyl group, or may be a group which forms a 5- or 6-membered hetero ring by bonding to ring A, and further has R ¹ and R ² bonded thereto. It may be a group which forms a 5- or 6-membered hetero ring together with a nitrogen atom, and R ³ and R ⁴ represent an electron-withdrawing group or a group which forms a ring by bonding with an adjacent carbon atom. Represents.) 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 or a CR ⁹
電子 C (CN) ₂ electron-withdrawing group selected from the group consisting of R ³ ,
Thermal transfer recording material according to claim 1 taken together with the carbon atom to which R ⁴ is adjacent a group capable of forming a heterocyclic ring selected from the following formulas. Embedded image (Wherein, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, an optionally substituted alkenyl group, an allyl group, Represents an alkyl group, R ⁹ represents a hydrogen atom, a cyano group, or a phenyl group which may be substituted, and R ¹⁰ , R ¹¹ , R ^11
13 and R ¹⁴ represent a hydrogen atom, an alkyl group which may be substituted, a phenyl group which may be substituted, an alkenyl group which may be substituted, an allyl group, and a cycloalkyl group; R ¹² represents a hydrogen atom; An alkyl group which may be substituted, an alkoxy group which may be substituted, a phenyl group which may be substituted, an alkylamino group which may be substituted, an alkoxycarbonyl group which may be substituted; ¹⁵ represents a cyano group or an 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 ²³ group (R
²³ is a hydrogen atom, a cyano group, an alkyl group, an alkoxy group,
Represents a cycloalkyl group, an aryl group, an amino group, an aralkyl group, or an aryloxy group), R ¹⁸ represents an oxygen atom, a C (CN) ₂ group, and R ¹⁹ , R ²⁰ , R ²¹ , and R ²² represent hydrogen. Atom, an optionally substituted alkyl group, a halogen atom, an optionally substituted alkylcarbonylamino group, an alkoxycarbonylamino group, an allylcarbonylamino group, an allyloxycarbonylamino group,
²¹ and R ²² may combine to form a ring. ) 3. A ring A in the general formula (I) is a benzene ring, a naphthalene ring, a pyridine ring and the following general formula (II):
(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, which is one selected from a heterocyclic ring 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.
Represents an optionally substituted alkyl group, an alkoxy group, a phenyl group optionally substituted with a halogen atom, or a group which forms a tetrahydroquinoline-based or dihydroindole-based ring by bonding to ring A , R ¹ and R ² form a morpholine ring, a piperazine ring and a thiomorpholine ring together with the nitrogen atom to which they are bonded.
Thermal transfer recording material described in 1. 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 recording medium 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. The thermal transfer recording material according to any one of claims 1 to 6, 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 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. Recording material. 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 an aromatic ring or a hetero ring which may have a substituent, and R ¹ and R ^{2 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, It may represent an unsubstituted phenyl group, an allyl group or a cycloalkyl group, or may represent a group which forms a 5- or 6-membered hetero ring by bonding to Ring A, and further has R ¹ and R ² bonded thereto. A group which forms a 5- or 6-membered hetero ring together with a nitrogen atom, and R ³ and R ⁴ each represent an electron-withdrawing group or a group which forms a ring by bonding with an adjacent carbon atom.)