JPH1035110A - Material and medium for thermal transfer recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the high quality recording by containing monofunctional monomers to be polymerized radically in which the glass transition temperature of a polymerized material is the temperature for recording or lower. SOLUTION: A thermal transfer recording material is composed of ultraviolet curing resin to be coated by emitting ultraviolet rays as light as a main component, and if required, a heat molten substance, a coloring agent and other very small amount of additives of approximately 0-10 pts.wt. are blended all together in the composition. Particularly monofunctional acrylic monomers or monofunctional methacrylic monomers performing the radical polymerization when ultraviolet rays are emitted, in which the glass transition temperature of a polymerized material is 0 deg.C or lower, are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material for forming an ink layer of a thermal transfer recording medium and a thermal transfer recording medium coated with the same, and more particularly to a thermal transfer recording material containing an ultraviolet curable resin and forming the same as an ink layer. To a thermal transfer recording medium that has been used.

[0002]

2. Description of the Related Art At present, various printers are used as output terminal devices of information processing apparatuses such as word processors, facsimile machines, computers, and the like. Various methods have been proposed.

[0003] Among these, silence, low cost,
In consideration of the miniaturization adaptability, easy operability, and high reliability, a thermal transfer method using a heating resistor element array called a thermal head has been widely used in the past, and in recent years, its use has been used for commercial purposes. From home use to hobby use.

The thermal transfer method uses a thermal transfer method in which ink on a thermal transfer recording medium is melted by the heat of a thermal head and transferred to recording paper made of plain paper, and a heat-sensitive paper which develops color by heat at or above a set temperature. The sublimation thermal transfer method, in which the thermal paper is colored by the heat of the thermal head, is used.
Although they can be broadly classified into types, from the viewpoint of price, the fusion thermal transfer recording method is currently the mainstream.

FIG. 5 shows the basic principle of the above-mentioned fusion type thermal transfer system and the basic configuration of the thermal transfer recording medium 1 used in this fusion type thermal transfer system. The so-called thermal transfer recording medium 1 has a structure in which an ink layer 7 is laminated on a base material 2.

As the substrate 2 of the thermal transfer recording medium 1, a polymer resin film having a film thickness of usually 1 to 12 μm is used. As the material of the substrate 2, polyethylene terephthalate, polyethylene naphthalate, polyimide ,
General-purpose resins such as polyetheretherketone and aramid are used.

On the back surface 2a of the base material 2, wear of the thermal head due to sliding contact is reduced, the running of the ink ribbon as the thermal transfer recording medium 1 is stabilized, and the ink ribbon is fused to the ink surface during winding. In general, a lubricating layer 5 is applied for the purpose of prevention or the like.

The ink layer 7 of the thermal transfer recording medium 1 is mainly composed of a hot-melt substance of wax or resin having good adhesion to recording paper, and various pigments and various plasticizers, dispersants, and oxidants as colorants. It is constituted by adding a small amount of an inhibitor or the like. Examples of the wax used in the ink layer 7 include carnauba wax, candelilla wax, rice wax, paraffin wax, microcrystalline wax, polyethylene wax, and the like, and these are used alone or in combination.

The heat-fusible resin used for the ink layer 7 includes ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and ethylene-acrylic ester copolymer. Examples thereof include poly (meth) acrylates such as polylauryl methacrylate and polyhexyl acrylate, and vinyl chloride copolymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl alcohol copolymer. These resins can be used alone or as a mixture.

When the thermal transfer recording medium 1 is formed, a hot-melt method is used, that is, an ink containing a hot-melt substance such as the wax as a main component is heated and applied to the substrate 2 in a molten state. It is formed by cooling and solidifying, or by the solvent method, that is, by immersing the substrate 2 in a resin solution or its dispersion and evaporating and removing the solvent to leave an adhered film.

[0011]

However, in the conventional thermal transfer recording medium 1, when it is formed by the hot melt method, it is necessary to always melt the ink, and the apparatus becomes large and the power consumption increases. There was a problem that it would. On the other hand, when formed by the solvent method,
It must be heated to provide the problem of solvent disposal and the heat of evaporation that removes the solvent, which consumes considerable energy for heating the air and other equipment required for this heating, such as electric furnaces. There was a problem.

On the other hand, in recent years, ultraviolet curable resins have attracted attention in the fields of paints and printing inks as resins having characteristics of no pollution and energy saving, and attempts have been made to use them for the thermal transfer recording medium 1. ing.

This UV-curable resin has few pollution problems, and usually requires no heating at the time of curing and only needs to irradiate UV rays, so that energy consumption is small. Has the advantage of being improved.

A photopolymerizable prepolymer is generally used as a commercially available ultraviolet curable resin. This is because, since it is a polymer in advance, it cures at a high speed when irradiated with ultraviolet rays, and it is possible to reduce costs such as minimizing the ultraviolet irradiation lamp, saving energy, and improving productivity.

However, even if a heat transfer material used for a thermal transfer ribbon is added to a general photopolymerizable prepolymer and applied to the base material 2 to form the thermal transfer recording medium 1, thermal transfer may not be performed. This is because the prepolymer has a small degree of polymerization, but has a network-like, so-called crosslinked structure as a polymer, and forms a more dense crosslinked structure as the ultraviolet curing reaction proceeds, so that heat is generated by the heat generated by the thermal head. This is because even if supplied, it does not melt. This is also reflected in the glass transition temperature. Many ultraviolet curing resins have a high glass transition temperature, and the recording obtained by the thermal transfer recording medium 1 shows that the ink layer 7 is cured when the glass transition temperature is high. There is a problem that recording cannot be performed at all in the state.

The present invention has been made in view of the above problems, and has as its object to provide a thermal transfer recording material and a thermal transfer recording medium which can easily form and reproduce an ink layer and can obtain good recording quality. It is assumed that.

[0017]

In order to achieve the above object, the thermal transfer recording material according to the first aspect of the present invention is characterized in that it undergoes radical polymerization by light and the glass transition temperature of the polymer is below the recordable temperature. And a hot-melt substance having a melting point or softening point within a recordable temperature range. By adopting such a configuration, it is possible to obtain high-quality recording when the curing speed is high and the ink layer is formed.

The thermal transfer recording material according to claim 2 is characterized in that the compounding amount of the monofunctional monomer is 10 to 80 parts by weight, the compounding amount of the hot-melt substance is 10 to 80 parts by weight, The point is that the compounding amount of the material is 1 to 25 parts by weight. Then, by adopting such a configuration, it is possible to more reliably obtain a high curing speed and high-quality recording when the ink layer is formed.

A feature of the thermal transfer recording material according to the third aspect is that the monofunctional monomer is an acrylic monomer or a methacrylic monomer. By adopting such a configuration, it is possible to obtain high-quality recording when the curing speed is high and the ink layer is formed.

The thermal transfer recording material according to claim 4 is characterized in that a monofunctional monomer which undergoes radical polymerization by light and has a glass transition temperature of the polymer at or below a recordable temperature, and a polymer which undergoes radical polymerization by light. It has a functional monomer and a hot-melt substance having a melting point or softening point within a recordable temperature range. By adopting such a configuration, it is possible to form an ink layer of a thermal transfer recording medium having a high curing rate and excellent heat fusibility.

The thermal transfer recording material according to claim 5, wherein the compounding amount of the monofunctional monomer is 10 to 80 parts by weight, the compounding amount of the polyfunctional monomer is 1 to 50 parts by weight, The amount of the molten material is 10 to 80 parts by weight, and the amount of the coloring material is 1 to 25 parts by weight. By adopting such a configuration, it is possible to more reliably provide a thermal transfer recording medium having an ink layer having a high curing rate and excellent heat fusibility.

A feature of the thermal transfer recording material according to claim 6 is that the monofunctional monomer and the polyfunctional monomer are acrylic monomers or methacrylic monomers. By adopting such a configuration, it is possible to obtain high-quality recording when the curing speed is high and the ink layer is formed.

A feature of the thermal transfer recording material according to claim 7 is that the monofunctional monomer has a glass transition temperature of 0 ° C. or less. By adopting such a configuration, high-quality recording can be performed more reliably as the ink layer of the thermal transfer recording medium.

The heat transfer recording material according to the present invention is characterized in that the heat-meltable substance is made of at least one of a wax or a heat-meltable resin having a melting point or a softening point within a temperature range of 50 ° C. or more and 100 ° C. or less. It is to be included. And by adopting such a configuration, the excellent melting property of the hot-melt substance can be more appropriately exhibited.

A feature of the thermal transfer recording material according to the ninth aspect is that at least one of a wax and a heat-fusible resin having a property of uniformly dispersing or dissolving the heat-fusible substance in the monofunctional monomer. The point is that one is included. And by adopting such a configuration, it is possible to maximize the excellent melting property of the hot melt material.

According to a tenth aspect of the present invention, there is provided a thermal transfer recording medium, wherein the ink layer is formed of a monofunctional monomer of the thermal transfer recording material according to any one of the first to ninth aspects.
Alternatively, it is constituted by forming a polymer by radically polymerizing a monofunctional monomer and a polyfunctional monomer with light. By employing such a configuration, it is possible to easily form and reproduce the ink layer and obtain good recording quality.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermal transfer recording material and the thermal transfer recording medium of the present invention will be described below with reference to embodiments shown in the drawings.

As shown in FIG. 1, a thermal transfer recording medium 1 of the present invention comprises an ink layer 4 made of a thermal transfer recording material 3 on a substrate 2.
Are laminated, and a back surface 2a of the base material 2 is provided.
Has a lubricating layer 5 formed thereon. The thermal transfer recording material 3 constituting the ink layer 4 has, as a main component, an ultraviolet curable resin which is cured by irradiating ultraviolet rays as light, and contains, if necessary, a heat melting substance, a colorant, and other trace additives.
The composition is about 10 to 10 parts by weight.

The substrate 2 of the thermal transfer recording medium 1 has a thickness of 0.1 mm.
A polymer resin film having a thickness of 5 to 20 μm, preferably 2 to 10 μm is used. If the thickness of the substrate 2 is less than 0.5 μm, the strength is insufficient, and if it is more than 20 μm, the sensitivity is insufficient, which is not preferable. As the material of the polymer resin film, polyethylene terephthalate, polyphenylene sulfide, polyimide, polyethylene naphthalate, polycarbonate, aramid and the like are suitable.

The lubricating layer 5 having a thickness of 1 μm or less, preferably 0.5 μm or less, is
Is formed with a fluorine-based or silicon-based coating agent. If the thickness is 1 μm or more, the sensitivity becomes insufficient, which is not preferable. This lubrication layer 5
, The wear of the thermal head due to the sliding contact is reduced, the running of the ink ribbon as the thermal transfer recording medium 1 is stabilized, and the fusion of the ink ribbon with the ink surface when the ink ribbon is wound can be prevented.

Next, an ultraviolet curable resin as a main component of the thermal transfer recording material 3 will be described.

First, the general UV-curable resin is composed of a photopolymerizable prepolymer, a photopolymerizable monomer, and a photoinitiator.
The photopolymerizable prepolymer is usually added in the range of 0 to 99 parts by weight, and is an important component constituting the skeleton of the resin.

The photopolymerizable prepolymer is a polymer which is further polymerized by a photochemical action, and is sometimes called a photopolymerizable unsaturated polymer or a photopolymerizable oligomer.

The photopolymerizable monomer plays a role of a diluent for the photopolymerizable prepolymer. Usually, the photopolymerizable monomer is added in an amount of 0 to 99 parts by weight to ensure practical workability of the ink. The terminal itself participates in the polymerization reaction by the action of the terminal functional group at the time of ultraviolet irradiation. The photopolymerizable monomer can be classified into a monofunctional monomer and a polyfunctional monomer according to the number of functional groups. Particularly, the polyfunctional monomer plays a role of a cross-linking agent that forms a bridge between polymers.

The photoinitiator absorbs ultraviolet rays and triggers a polymerization reaction.

Among the general UV-curable resins having the above-described structure, the UV-curable resin according to the first embodiment of the present invention particularly plays a role of the photopolymerizable monomer and the photopolymerizable prepolymer. For example, a monofunctional acrylic monomer or a monofunctional methacrylic monomer (also referred to as a methylacrylic monomer) having a glass transition temperature of 0 ° C. or lower is used for a radical polymerization reaction when irradiated with ultraviolet rays.

The amount of these monomers in the recording material for thermal transfer is 10 to 80 parts by weight, preferably 40 to 80 parts by weight.

Here, the glass transition temperature is a temperature at which the state changes from a viscous region or an elastic region to a hard amorphous region, and this temperature depends on the compounding ratio of the ultraviolet curable composition, the curing temperature, and the like. The temperature to be determined.

The reason why the monofunctional monomer is used is that the structure is simple and the heat melting property is excellent when the polymer is obtained by irradiating light. On the contrary,
The polymer of the polyfunctional monomer has a dense crosslinked structure, and does not easily melt by the heat generated by the thermal head.

Further, the reason for using acrylic monomers and methacrylic monomers as monofunctional monomers is that they are generally available at low cost and are superior to other monomers in that the polymerization rate (curing rate) is high. .

With respect to various acrylic monomers and methacrylic monomers, an experiment was conducted to determine how the glass transition temperature affects the recording quality. Table 1 shows the experimental results.

[0042] Table 1 shows the state of recording quality when recording was performed using the thermal transfer recording medium 1 in which an ink layer contains polymers of monomers having various glass transition temperatures. 2-Ethylhexyl acrylate, methoxypropylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate in Table 1,
Lauryl methacrylate, 3-methoxybutyl acrylate, 2-methoxyethyl acrylate, hydroxyethyl acrylate, n-hexyl methacrylate, lauryl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, ethyl methacrylate, and isopropyl methacrylate are monofunctional acrylic monomers or monofunctional methacrylic monomers It is. According to Table 1, it can be seen that the recording quality in the case where the ink layer was formed using an acrylic monomer having a glass transition temperature of 0 ° C. or less as an ultraviolet curable resin was in a good condition. In this experimental result, almost the same results were obtained for a methacrylic monomer having a glass transition temperature of 0 ° C. or lower.

However, when an ink layer was formed by using an acrylic monomer or a methacrylic monomer having a glass transition temperature of 0 ° C. or higher as an ultraviolet curable resin, the recording quality was blurred or impossible.

Therefore, the glass transition temperature of the polymer is 0
The acrylic monomer and the methacrylic monomer having a temperature of not higher than 0 ° C. will form an ink layer 4 suitable as the thermal transfer recording medium 1. It can be seen that the layer 4 can be formed. If the polymer is at 0 ° C
When having the above glass transition temperature, thermal transferability is inferior, because a low melting point wax or a resin having a low softening point must be used as the heat melting substance,
The recording state is liable to be stained or crushed.

The above-mentioned radical polymerization reaction is one of ultraviolet curing reactions. This reaction requires a photoinitiator and usually includes a start reaction, a growth reaction, a chain transfer reaction and a termination reaction. Divided into reactions. Among these, the initiation reaction is a reaction that activates the photoinitiator and generates radicals to activate the photopolymerizable monomer when the ultraviolet curable composition is irradiated with ultraviolet rays. The main methods for activating the photoinitiator include photocleavage, hydrogen abstraction, and electron transfer. In addition, the growth reaction refers to a reaction in which the degree of polymerization of the radical generated in the initiation reaction gradually increases, and the chain transfer reaction refers to a reaction in which the radical is transferred to another molecule. The terminating reaction refers to a reaction in which radicals disappear and the radical reaction ends.

On the other hand, in the ultraviolet curable resin of the first embodiment, the monofunctional acrylic monomer or the monofunctional methacryl monomer is used, and the photopolymerizable prepolymer is not blended. However, a desired effect can be sufficiently obtained with only these monofunctional monomers. Note that, depending on the type of the monofunctional monomer, a small amount of the photopolymerizable prepolymer may be used to improve the polymerization rate.

Examples of the photoinitiator include biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, tetramethylthiuram sulfide, azobisisobutylnitrile, benzoyl peroxide, di-tert-butyl. Peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
-(4-isopropylphenyl) -2-hydroxy-2
-Methylpropan-1-one, 2-chlorothioxanthone, methylbenzoylformate and the like can be mentioned as preferable examples.

Next, a heat-fused material will be described as another component of the thermal transfer recording material 3.

The hot-melt substance is classified into wax and resin. Common waxes include petroleum waxes such as paraffin, vegetable waxes such as carnauba and candelilla, animal waxes such as beads, coal waxes such as montan, and synthetic waxes such as Fischer-Tropsch. In addition, as general resins, low molecular weight polyethylene, ethylene-vinyl acetate, ethylene-
There is a hot-melt or softening resin such as ethyl acrylate.

Here, in order to determine a heat-fusible material suitable as the thermal transfer recording material 3, the effect of the melting point of the heat-fusible material on the recording quality, an experiment on the dispersibility or compatibility of the heat-fusible material with a monofunctional monomer, Experiments were conducted on the effect of dispersibility and compatibility with the acrylic monomer on the ink curing time. Tables 2 to 7 show the results of these experiments.

Tables 2 and 3 show the relationship between the melting point of the hot-melt material and the recording quality among the experimental results. Of the hot-melt substances, wax is shown in Table 2, and resin is shown in Table 3.

[0052] As can be seen from Table 2, when the ink layer 4 contains deodorized jojoba oil having a melting point of normal temperature and paraffin wax having a melting point of 47 ° C., the ink becomes too soft and is transferred and stained only by rubbing with the recording paper. Will be.

Further, oxidized microcrystalline wax having a melting point of 106 ° C. or 116 ° C. and a melting point of 105 ° C.
When the ink layer 4 contained a uniline alcohol derivative or an α-olefin derivative having a melting point of 121 ° C., the recording was faint or could not be performed at all. This is because the heat capacity of the ink becomes too large and the ink cannot be melted by the heat generated by a normal thermal head.

In contrast, when the ink layer 4 contained an oxidized microcrystalline wax having a melting point of 85 ° C. and a unilin alcohol derivative having a melting point of 78 ° C., an extremely good recording state was obtained. A good recording state was obtained even in the case of the uniline alcohol derivative having a melting point of 99 ° C. This is because even if the calorific value of the thermal head is transmitted through the base material 2, it can be sufficiently melted.

Therefore, a wax having a melting point of about 50 to 100 ° C. is preferable as the heat-fusible substance constituting the thermal transfer recording material 3.

On the other hand, the relationship between the softening point of the resin-based hot-melt material shown in Table 3 and the recording quality shows the same tendency as the result shown in Table 2.

That is, when glycerin having a softening point of 18 ° C. and lauric acid having a softening point of 44 ° C. were contained in the ink layer 4, the result was that the recording paper was soiled.

When the ink layer 4 contained a polyester resin having a softening point of 100 or more, the recording was blurred or impossible.

However, ketone resins having a softening point of 78 ° C. or 85 ° C., ethylene / acrylic acid resins having a softening point of 64 ° C. or 87 ° C., polyester resins having a softening point of 86 ° C., rosin derivatives having a softening point of 75 ° C., When the ink layer 4 contained a terpene derivative having a softening point of 80 ° C., good or very good recording quality could be obtained.

Accordingly, it has been found that a heat-melting substance having a softening point within a temperature range of about 50 to 100 ° C. is suitable as the heat-melting substance constituting the thermal transfer recording material 3.

According to Tables 2 and 3 above, the thermal transfer material constituting the thermal transfer recording material 3 is good when the thermal transfer recording material 3 is thermally transferred and recorded as the ink layer 4 of the thermal transfer recording medium 1. A hot-melt substance having a melting point or softening point that provides excellent recording quality is preferred. Specifically, a heat-meltable resin having a melting point or softening point of 50 to 100 ° C is preferable. In this case, the hot-melt material is not limited to a wax-based material and a resin-based material alone, and may be a mixed-type hot-melt material obtained by mixing both.

Next, the results of experiments on the dispersibility or compatibility of the hot-melt substance with respect to the monofunctional monomer will be described.

Here, an experimental method of dispersibility and compatibility will be described. An acrylic monomer was used as the monofunctional monomer, and various waxes and hot-melt resins were used as the hot-melt material. The weight ratio of the acrylic monomer and each hot-melt substance is set to 80:20 (parts by weight) and put into a beaker. The temperature is raised to the melting point or higher in the case of wax, and to the softening point or higher in the case of the hot-melt resin. Thereafter, the mixture is heated and melted for 30 minutes by a motor stirrer equipped with a slide rack and a mantle heater. Thereafter, stirring was continued until the temperature reached room temperature, and the state of dispersibility or compatibility was observed. The experimental results for the wax are shown in Table 4, and the experimental results for the hot-melt resin are shown in Table 5.

[0064] As shown in Table 4, in the case of petroleum-based, plant-based, animal-based, and coal-based waxes such as paraffin wax, carnauba wax, candelilla wax, beeswax, rice wax, montan wax, and jojoba oil, acrylic monomers are used. Were poor in dispersibility, and each was in a separated state.

On the other hand, in the case of synthetic waxes such as oxidized microcrystalline wax, polyethylene oxide wax, uniline alcohol derivative, α-olefin derivative and maleic acid derivative, the dispersibility with the acrylic monomer is good and uniform. It became a dispersed state.

On the other hand, the experimental results of the heat-meltable resin are shown in Table 5, which shows that the vinyl chloride resin, petroleum resin, polyamide resin, polyethylene resin, polypropylene resin and polystyrene resin have poor compatibility with the acrylic monomer. Did not dissolve.

On the other hand, in the case of the polyester resin, ketone resin, ethylene / ethyl acrylate resin, ethylene / vinyl acetate resin and rosin derivative, the state was good in compatibility with the acrylic monomer.

Next, an experiment was conducted to determine how the results of dispersibility or compatibility shown in Tables 4 and 5 affect the curing time of the thermal transfer recording material 3. The experimental conditions were as follows: 8 mw / cm ² ultraviolet rays were irradiated in an aerobic atmosphere.

Table 6 shows the relationship between the difference in the dispersibility of the wax in the acrylic monomer and the curing time of the thermal transfer recording material 3. Table 7 shows the difference in the compatibility of the heat-fusible resin in the acrylic monomer and the thermal transfer recording material. 3 shows the relationship with the curing time.

[0070] As is clear from Table 6, the thermal transfer recording material 3 containing paraffin wax, carnauba wax, candelilla wax, and beeswax, which has poor dispersibility with the acrylic monomer, takes at least 5 minutes or more to cure by irradiation with ultraviolet rays. Some required 20-30 minutes.

On the other hand, oxidized microcrystalline wax, polyethylene oxide wax, unilin alcohol derivative, α-
The result that the thermal transfer recording material 3 containing the olefin derivative was cured within 2 to 3 minutes after being irradiated with the ultraviolet rays was obtained.

From the experimental results shown in Table 6 above, it can be seen that a wax having good dispersibility with a monofunctional monomer has less effect on a delay in curing speed of the thermal transfer recording material 3 than a wax having poor dispersibility. all right.

On the other hand, when the experimental results of the hot-melt resin shown in Table 7 were observed, the same tendency as the experimental results of the wax in Table 6 was observed. That is, the thermal transfer recording material 3 containing a vinyl chloride resin, a petroleum resin, a polyamide resin, and a polyethylene resin having poor compatibility with the acrylic monomer takes 3 to 4 minutes or more to cure by irradiation with ultraviolet rays, and in some cases, 10 to 10 minutes. Some resins took more than a minute.

On the other hand, polyester resins, ketone resins, and ethylene resins having good compatibility with acrylic monomers
It was found that the thermal transfer recording material 3 containing the ethyl acrylate resin and the rosin derivative completed curing within 1 to 2 minutes after being irradiated with ultraviolet rays.

From the experimental results shown in Table 7 above, it is clear that a resin having good compatibility with the monofunctional monomer has less influence on the delay of the curing speed of the thermal transfer recording material 3 than a resin having poor compatibility. all right.

That is, according to the experimental results in Tables 4 to 7, the hot-melt substance usually does not participate in the polymerization reaction and hinders the polymerization reaction, which may hinder the curing. Alternatively, a hot-melt substance having a compatible property can maintain the high-speed curability characteristic of an ultraviolet curable resin without a problem of curing inhibition.

From the above experimental results on the hot-melt substance,
A heat-melting substance suitable as the thermal transfer recording material 3 is a heat-melting substance having a melting point or a softening point such that good recording quality is obtained when the thermal transfer recording material 3 is thermally transferred and recorded as the ink layer 4 of the thermal transfer recording medium 1. It is a hot-melt substance that has the property of being uniformly dispersed or compatible with the monofunctional monomer. Specifically, the melting point or softening point of the hot-melt substance is preferably 50 to 100C. In this case, the hot-melt substance is not limited to the wax or hot-melt resin alone, and may be a mixed hot-melt substance obtained by mixing both the wax and the hot-melt resin.

The compounding amount of the hot-melt substance is 10
-80 parts by weight, preferably 10-50 parts by weight.

Next, the coloring material constituting the thermal transfer recording material 3 will be described. Examples of the colorant include black pigments such as carbon black, acetylene black and oil black and white pigments such as titania and calcium carbonate, as well as known dyes such as yellow, magenta and cyan. Alternatively, the color tone or the like is adjusted to a desired state by appropriately changing the amount of the dye added. Specifically, the amount is 1 to 25 parts by weight, preferably 5 to 20 parts by weight. When the amount is 1 part by weight or less, the coloring power becomes insufficient, and when the amount is 25 parts by weight or more, the coating agent becomes powdery and can be applied as it is. Will be gone.

Examples of the trace additives to be added to the thermal transfer recording material 3 include oils such as silicone oil, liquid waxes such as jojoba oil, and dispersants. The compounding amount is 0 to 20 parts by weight, preferably 0 to 10 parts by weight. If the oil is added in an amount of 20 parts by weight or more, it is not preferable because stains are easily generated during recording.

The thermal transfer recording material 3 may further contain additives such as a sensitizer, a filler and a leveling agent, if necessary.

Next, a manufacturing apparatus 10 for manufacturing the thermal transfer recording medium 1 by applying the thermal transfer recording material 3 to the substrate 2.
The manufacturing method will be described with reference to FIG.

FIG. 2 shows the inside of a manufacturing apparatus 10 for the thermal transfer recording medium 1. A base supply reel 11 for supplying the base 2 of the thermal transfer recording medium 1 and an ink are provided at both ends of the manufacturing apparatus 10. A ribbon reel 12 that holds the thermal transfer recording medium 1 on which the layer 4 is formed is provided. The thermal transfer recording medium 1 is transported at a constant speed by a drive mechanism (not shown).

A heating type recording material tank 13 is provided below the base material supply reel 11 and is filled with the thermal transfer recording material 3. A recording material supply roller 14 is disposed in the heating type recording material tank 13 so as to be immersed in the thermal transfer recording material 3 inside. The base material 2 is pressed against the recording material supply roller 14.

A film thickness control device 15 having a blade or a knife is movably disposed in the vicinity of the recording material supply roller 14 and on the conveyance path of the substrate 2. The thickness of the thermal transfer recording material 3 applied to the base material 2 is made uniform by moving the blade or the like of the film thickness control device 15 in parallel with the base material 2.

An ultraviolet irradiator 16 is provided on the back side 2a of the substrate 2 so that the thermal transfer recording material 3 applied to the substrate 2 is cured by the ultraviolet rays to be irradiated. I have. As a light source of the ultraviolet irradiator 16, a mercury lamp, a mercury xenon, a metal halide lamp, or the like is used.

A cleaning roller 17 is provided between the ultraviolet irradiator 16 and the ribbon roll.
Is to be wiped off.

Next, a method for manufacturing the thermal transfer recording medium 1 will be described.

First, the respective materials constituting the above-mentioned thermal transfer recording material 3 are mixed using a usual stirrer at a temperature at which the hot-melt substance is melted. Then, this is cooled to room temperature, and then milled by an ordinary dispersing machine such as a three-roll mill to produce the thermal transfer recording material 3. During the milling, heating may be performed slightly to improve the dispersion efficiency.

Then, the thermal transfer recording material 3 is placed in the heating type recording material tank 13 and heated. In the heating type recording material tank 13, the recording material supply roller 1
When the rotary member 4 is driven to rotate, the thermal transfer recording material 3 is attached to the outer peripheral surface of the recording material supply roller 14 and is pumped up.
The pumped-up thermal transfer recording material 3 is applied to one entire surface of the substrate 2 carried out by the substrate 2 supply reel.
After the thermal transfer recording material 3 applied to the base material 2 is formed to a constant film thickness by the blade of the film thickness control device 15, the ultraviolet irradiator 16 irradiates ultraviolet light from the back side 2 a of the base material 2. I do. Thereby, the thermal transfer recording material 3 is cured by the polymerization reaction, and the ink layer 4 can be formed. Then, after the excess heat transfer recording material 3 that has not been cured by the ultraviolet irradiation is removed by the cleaning roller 17, the formed heat transfer recording medium 1 is wound up by a ribbon roll.

In the method for manufacturing the thermal transfer recording medium 1, the thermal transfer recording material 3 is heated in the heating type recording material tank 13 before the thermal transfer recording material 3 is applied to the substrate 2.
It is not necessary to limit to this, and it is sufficient that the heating is performed at the time of irradiation with the ultraviolet light. For example, a heating device such as applying hot air after applying the thermal transfer recording material 3 to the base material 2 or passing over the surface heating element may be used.

The ultraviolet irradiation by the ultraviolet irradiator 16 is performed from the back side 2a of the substrate 2, but may be performed from the ink layer side. According to this method, the entirety of the thermal transfer recording material 3 can be cured and no extra thermal transfer recording material 3 remains, so that a cleaning step is not required.

Further, at the time of ultraviolet irradiation by the ultraviolet irradiator 16, the surface of the ink layer 4 may be made to have an anaerobic atmosphere by an anaerobic device (not shown) to carry out a polymerization reaction. According to such a method, the curing speed can be further improved.

The method and apparatus 10 for manufacturing the thermal transfer recording medium 1 described above can be applied as a reproducing apparatus 18 for reproducing the used thermal transfer recording medium 1. This playback device 18
The reproducing method and the reproducing method will be described with reference to FIGS.

FIG. 3 is a schematic diagram showing a reproducing apparatus 18 of the thermal transfer recording medium 1 used in the first embodiment.

Usually, in the ribbon cassette 19 containing the thermal transfer recording medium 1 such as an ink ribbon, the thermal transfer recording medium 1 is guided by a plurality of guide rollers 22 so that the thermal transfer recording medium 1 can run stably in the ribbon cassette 19. The traveling of the ribbon cassette 19 is controlled, and a concave portion for positioning a thermal head (not shown) during a recording operation is provided in a portion of the ribbon cassette 19 indicated by A in the drawing.

The reproducing device 18 is provided with a mounting portion 20 for mounting a ribbon cassette 19 containing the thermal transfer recording medium 1 that has been used once and needs to be reproduced. When the ribbon cassette 19 is mounted on the mounting portion 20, a tension head 21 is installed at a portion facing the recess A of the mounted ribbon cassette 19. The tension head 21 is moved up and down in FIG. 3 by driving means (not shown). On the other hand, in FIG. 3, a recording material tank 13 is disposed immediately below the concave portion A of the ribbon cassette 19 mounted on the mounting portion 20 described above, and in the recording material tank 13, the above-described liquid thermal transfer recording is performed. Material 3 is filled. Further, a recording material supply roller 14 which is driven to rotate by driving means (not shown) is provided in the recording material tank 13. The thermal transfer recording material 3 is attached to the outer peripheral surface and is pumped up.

Then, the ribbon cassette 19 is placed in the
, The tension head 21 moves to a position B separated from the recess A of the ribbon cassette 19 by several millimeters to several centimeters. As a result, the thermal transfer recording medium 1 is pulled out of the ribbon cassette 19 while being hooked by the tension head 21, and the surface thereof is pressed against the recording material supply roller 14. At this time, the base material of the thermal transfer recording medium 1 comes into contact with the tension head 21, and the ink layer formed on the thermal transfer recording medium 1 and solidifying the thermal transfer recording material 3 comes into contact with the recording material supply roller 14. In the vicinity of the recording material supply roller 14, a film thickness control device 15 including a blade for uniformly controlling the film thickness of the thermal transfer recording material 3 applied to the thermal transfer recording medium 1 by the recording material supply roller 14 is provided. Is provided.

The tension head 2 is located on both sides of a substantially intermediate portion of the movement path of the tension head 21.
A guide roller 22 and a cleaning roller 17 are provided at right and left intervals so as not to interfere with the thermal transfer recording medium 1 pulled out of the ribbon cassette 19 while being hooked on the guide roller 22. Furthermore, these two rollers 1
At a portion where a virtual line connecting the lines 7 and 9 intersects with the movement path of the tension head 21, there is provided a traveling unit 23 which can be moved forward and backward by moving in a direction perpendicular to the plane of the drawing by driving means (not shown). It is arranged. The traveling unit 23 includes a pair of tension rollers 24, 24 elastically pressed against one of the two rollers 17, 9 when located at an advanced position located on the same vertical plane as the two rollers 17, 9. It has a movable back and forth.

The thermal transfer recording medium 1 runs in the direction of the arrow in FIG. 3, and the thermal transfer recording medium 1 comes into contact with the recording material supply roller 14 and then with the cleaning roller 17. ing.

Further, an ultraviolet irradiator 16 for solidifying the thermal transfer recording material 3 is provided inside the thermal transfer recording medium 1 so as to face the base material of the thermal transfer recording medium 1 between the recording material supply roller 14 and the cleaning roller 17. It is arranged in. Further, a heating device 25 for annealing the thermal transfer recording material 3 on the thermal transfer recording medium 1 is provided downstream of the cleaning roller 17 in the running direction of the thermal transfer recording medium 1. 3 are disposed so as to be opposed.

Next, the operation of the reproducing device 18 will be described.

The ribbon cassette 19 is mounted on the mounting portion 20, the tension head 21 is moved from A to B in FIG. 3, the thermal transfer recording medium 1 is hooked on the tension head 21 and pulled out from the ribbon cassette 19, and Is pressed against the recording material supply roller 14.
Next, the traveling unit 23 at the evacuation position is moved in the direction perpendicular to the plane of the paper to stop at the advanced position, and then the pair of tension rollers 24, 24 supported by the traveling unit 23 are moved to the guide roller 22 and the cleaning roller. The roller 17 is pressed against the roller 17. Thus, the preparation of the traveling system of the thermal transfer recording medium 1 is completed by sandwiching the thermal transfer medium 1 between the tension roller 24 and the guide roller 22 and between the tension roller 24 and the cleaning roller 17, respectively.

In this state, the winding bobbin 26 of the ribbon cassette 19 is rotationally driven by a driving means (not shown) provided in the reproducing device 18 so that the thermal transfer recording medium 1 travels in the direction shown by the arrow C in the figure. . And
As the thermal transfer recording medium 1 travels, the ink supply roller 12
After the thermal transfer recording material 3 is entirely coated on the surface of the thermal transfer recording medium 1 by the method, the film thickness of the thermal transfer recording material 3 applied on the thermal transfer recording medium 1 is uniformly controlled by the film thickness control device 15, and then the ultraviolet light is applied. Thermal transfer recording medium 1 by irradiator 16
By irradiating ultraviolet rays from the back side 2a of the above, only the thermal transfer recording material 3 applied to the ink deficient portion 4a is solidified, and the ink layer is reproduced on the portion which has become the ink deficient portion 4a.

Thereafter, of the thermal transfer recording material 3 applied to the surface of the thermal transfer recording medium 1, the excess material which is applied to the portions other than the ink deficient portion 4 a, that is, the places where the ink layer remains, and is not solidified by the irradiation of ultraviolet rays. Is removed by the cleaning roller 17. After that, the boundary portion 6 between the ink layer on the thermal transfer recording medium 1 reproduced by the annealing treatment by the heating device 25 and the ink layer remaining on the thermal transfer recording medium 1 is eliminated, thereby forming a series of thermal transfer recording media 1. The regeneration process is completed.

In this embodiment, the description has been made by taking the thermal transfer recording medium 1 having a single ink layer as an example. However, by adjusting the irradiation conditions of the ultraviolet light in the reproducing method of the present invention, the multi-time ribbon or the like can be used. It is needless to say that the present invention can be applied to reproduction of the thermal transfer recording medium 1 having a laminated structure.

Next, a method of reproducing the thermal transfer recording medium 1 will be described with reference to FIG.

The method of reproducing the thermal transfer recording medium 1 is shown in FIG.
In order to reproduce a used ink ribbon as shown in (A) so that it can be used again, a step of applying the thermal transfer recording material 3 having the above-described structure to the entire surface of the thermal transfer recording medium 1 including the ink deficient portion 4a ( 4 (B), a step of curing the thermal transfer recording material 3 applied in the ink deficient portion 4a by irradiating ultraviolet rays from the back side 2a of the thermal transfer recording medium 1, that is, from the substrate 1a side (FIG. 4 (C)). )), And thereafter, a cleaning step (FIG. 4D) for removing excess thermal transfer recording material 3 applied to portions other than the ink deficient portions 4a. In particular, in the case of reproducing the thermal transfer recording medium 1 for performing high-definition printing, an annealing step in which the boundary 6 between the reproduced ink layer 2a and the remaining ink layer 1b is eliminated by melting the ink. (FIG. 4E) is further added.

More specifically, in FIG. 4A, the thermal transfer recording medium 1 such as a used ink ribbon and an ink sheet has an ink layer 1b remaining on the substrate 1a and not used for printing. doing. On the base material 1a between the pair of ink layers 1b, 1b, an ink deficient portion 4a is formed because the ink layer is transferred and recorded on the recording paper.

In order to reproduce the used thermal transfer recording medium 1, first, in the step shown in FIG. 4B, the recording material supply roller 14 is used to remove the coating ink 2 made of the thermal transfer recording material 3 including the ink deficient portion 4 a. The thermal transfer recording medium 1 is applied over the entire surface. Thereafter, the coating ink 2 is moved by moving a film thickness control device 15 such as a knife or a blade.
To make the film thickness uniform. Here, the film thickness of the applied ink 2 to be applied is ideal as long as it is equal to the film thickness of the ink defective portion 4a. However, even if the applied amount is excessive as in this embodiment, the untransferred ink layer 1b There is no problem because the ink adhering to the surface can be removed by a cleaning step described later.

Next, in the step shown in FIG.
The entire surface of the thermal transfer recording medium 1 on which the coating ink 2 is applied, that is, the back surface 2a, is irradiated with ultraviolet light from the ultraviolet light irradiator 16 from the back side 2a.

Even after the ultraviolet irradiation, the untransferred remaining ink layer 1b has already solidified, so that there is no change, and the coating ink 2 applied on the untransferred ink layer 1b is irradiated. Ink layer 1 to which ultraviolet rays have not been transferred
Since it is blocked by b and does not penetrate to the surface, it does not cause a polymerization reaction by ultraviolet rays and maintains a liquid state.

On the other hand, the coating ink 2 applied to the ink deficient portion 4a is irradiated with the ultraviolet light transmitted through the translucent base material 1a, so that a polymerization reaction occurs and the coating ink 2 is cured to form the ink layer 2a.
Will be played as

As described above, the thermal transfer recording medium 1 of this embodiment
According to the regenerating method, it is possible to only cure the applied ink 2 existing in the ink defective portion 4a.

The ink layer 2a to be reproduced has a thickness of:
It can be appropriately controlled depending on curing conditions such as ultraviolet irradiation time, power and wavelength, and characteristics of the material used.

Next, in the cleaning step shown in FIG. 4D, the excess coating ink 2b (FIG. 4) which did not react and was not cured in the ultraviolet irradiation step shown in FIG.
(See (C)) is wiped off by the cleaning roller 17 and removed, thereby completing the one-cycle regeneration process.

When the thermal transfer recording medium 1 for performing high-definition printing is reproduced, it is necessary to further repair the boundary 6 between the remaining ink layer 1b and the newly reproduced ink layer 2a. In the case where there is, as shown in FIG. 4E, an annealing step of performing a heating annealing process from the surface side of the ink layer 1b using a heating device 25 such as a halogen lamp is further added, so that the boundary portion 6 The boundary 6 may be eliminated by dissolving the ink layers. As a means for performing the heat annealing treatment, in addition to the above-described non-contact heating method using a halogen lamp light source, a contact heating method using a thermal head can be used.

This annealing step is effective as a means to be used together when extremely high-definition printing of a photographic image or the like is required. In the case of ordinary character printing or the like, there is no problem even if it is omitted.

Next, the first embodiment of the thermal transfer recording material 3 and the thermal transfer recording medium 1 of the present invention will be described with reference to specific examples.

In the present embodiment, a polyimide film having a thickness of 7.5 μm was used as the polymer resin film of the base material 2, and a glass transition was used as the monofunctional acrylic monomer as the main component of the thermal transfer recording material 3. Temperature of -67 ° C 2
-65 parts by weight of ethyl carbitol acrylate, and an acetophenone-based compound as a photoinitiator was used.
0 parts by weight, melting point of 86 ° C
10 parts by weight of the polyester resin and 5 parts by weight of a rosin derivative having a melting point of 75 ° C., and 10 parts by weight of carbon black as the coloring agent.

Then, in order to produce the thermal transfer recording material 3, a monofunctional monomer, 2-ethyl carbitol acrylate, and a photoinitiator among the above-mentioned components constituting the thermal transfer recording material 3 were placed in a beaker. Then, the mixture is stirred and melted by a motor stirrer provided with a mantle heater and a slide rack. Next, the polyester resin and the rosin derivative, which are the above-mentioned hot-melt substances, are added and stirred by heating to melt, and then carbon black is further added and mixed by stirring with heating for 30 minutes. This was cooled to room temperature while stirring, and then milled by a three-roll mill to produce a desired thermal transfer recording material 3.

Then, in order to form an ink ribbon as the thermal transfer recording medium 1, the thermal transfer recording material 3 prepared above was used.
Was poured into a paint pan serving as a recording material tank 13, and a 3 μm-thick polyimide film (manufactured by Ube Industries, Ltd.) having a thickness of 7.5 μm and subjected to back treatment with Cymac US350 (methyl ethyl ketone solution) using an offset gravure coating machine. The ink layer 4 is formed by coating so as to have a thickness. A fluororesin film having a thickness of 100 μm is attached to and adhered to the coated surface. Furthermore, a hot plate heated to 80 ° C. or higher, which is the melting point of the hot-melt substance, is applied to the fluororesin film surface, and 8 mw / cm ² ultraviolet rays are applied from the back side 2 a of the polyimide film by a high-pressure mercury lamp for 10 seconds. Irradiate. This irradiation caused the thermal transfer recording material 3 to undergo a polymerization reaction and cure, thereby producing an ink ribbon as the thermal transfer recording medium 1.

When this ink ribbon was mounted on a thermal transfer printer (manufactured by Star Seimitsu Co., Ltd.) of SJ-144 (resolution: 400 dpi, recording was performed on a word processor paper for thermal transfer (manufactured by Union Chemical Co., Ltd.). .5, and an image with good edge reproducibility was obtained.

Then, the used ink ribbon is set in the reproducing device 18 for the thermal transfer recording medium 1 shown in FIG. 3, and the thermal transfer recording material 3 is applied and irradiated with ultraviolet rays by the above-mentioned reproducing method to thereby form the ink defective portion 4a. Was played. Unwanted unreacted ink was removed with a knife or blade. This cleaning may be performed by a dry cleaning method.

When the thus reproduced ink ribbon was mounted on the thermal transfer printer and recording was performed again, the image density became 1.4, and a good edge reproduction which was comparable to the previous recorded image was obtained. Sex was obtained.

According to the above-described first embodiment of the thermal transfer recording material 3 and the thermal transfer recording medium 1 of the present invention, since an ultraviolet curable resin is used as the thermal transfer recording material 3, It is only necessary to irradiate the surface with ultraviolet light, so that the ink layer can be easily formed and the reproduction is easy. In addition, the recording state after reproduction can be of good quality.

Next, a second embodiment of the present invention will be described.

Note that, of the configuration of the second embodiment, the same configuration as that of the above-described first embodiment will not be described again, and the configuration different from that of the first embodiment will be described in detail. I decided to.

The heat transfer recording material 3 in the second embodiment
In addition, the thermal transfer recording medium 1 is composed of a monofunctional monomer having a glass transition temperature of 0 ° C. or lower and a monofunctional monomer having a glass transition temperature of 0 ° C. or less, as an ultraviolet curable resin which is a main composition of the composition constituting the thermal transfer recording material 3. And a polyfunctional monomer that undergoes radical polymerization. The blending amount of the monofunctional monomer in the recording material for thermal transfer is 10
The amount is from 80 to 80 parts by weight, preferably from 40 to 80 parts by weight, and the blending amount of the polyfunctional monomer is from 1 to 50 parts by weight, preferably from 5 to 30 parts by weight.

Then, the ultraviolet curable resin is subjected to radical polymerization to form the ink layer 4 of the thermal transfer recording medium 1.
To form

The monofunctional monomer is excellent in thermal transferability because it does not form a dense crosslinked structure even when polymerized and is easily melted by heat. However, the monofunctional monomer alone has poor curability, and therefore has a property contrary to high-speed curing. Have.

On the other hand, the polyfunctional monomer, when polymerized, has a dense crosslinked structure and thus has poor heat melting property, and may not be able to be transferred by the heat generated by the thermal head, but has good curability and cures at high speed.

Accordingly, in the present invention, a very small amount of a bifunctional or trifunctional monomer whose polymer structure does not form a dense crosslinked structure among monofunctional monomers and polyfunctional monomers is added as an ultraviolet curable resin, so The thermal transfer recording material 3 utilizing the curability was produced.

Here, an experiment was conducted on the relationship between the rate of addition of the polyfunctional monomer to the thermal transfer recording material 3 and the curability and thermal transferability of the thermal transfer recording material 3. In this experiment, 2-ethylhexyl carbitol acrylate was used as a monofunctional monomer, and diethylene glycol diacrylate as a bifunctional monomer or trimethylolpropane triacrylate as a trifunctional monomer was added to the total weight of the thermal transfer recording material 3 as a polyfunctional monomer. 5, 10, 20, and 50 parts by weight. Table 8 shows the curing time of the thermal transfer recording material 3 produced for each addition ratio and the quality of recording obtained using the cured ink.

[0135] According to Table 8, when 2-ethylhexyl carbitol acrylate, which is a monofunctional monomer, is used alone, the curing time of the thermal transfer recording material 3 is 5 minutes, and the thermal transfer recording material 3 is used as the ink layer 4 for thermal transfer recording. As a result of recording with the medium 1, good recording quality was obtained.

The curing time of the thermal transfer recording material 3 using 5 parts by weight and 10 parts by weight of the 2-ethylhexyl carbitol acrylate and diethylene glycol diacrylate as a bifunctional monomer was shortened to 3 minutes and 2 minutes, respectively. Good recording quality was obtained in the range.

However, when the addition rate of diethylene glycol diacrylate was increased to 20 parts by weight and 50 parts by weight, the curing speed of the thermal transfer recording material 3 was increased, and
It cures in 0 seconds and 5 seconds. However, the recording state has been blurred, and the ink has not melted and cannot be recorded.

The curing time of the thermal transfer recording material 3 using 5 parts by weight of the 2-ethylhexyl carbitol acrylate and trimethylolpropane triacrylate, which is a trifunctional monomer, is 3 minutes each, and the recording state in this range is good. Quality was able to be obtained.

However, if the addition ratio of trimethylolpropane triacrylate is 10 parts by weight, the curing time is 1
And the curing speed increases, but the recording state is blurred. When the addition amount is further increased to 20 parts by weight and 50 parts by weight, the curing time of the thermal transfer recording material 3 becomes 15 minutes each.
The curing speed was further increased to seconds and 5 seconds, but no recording was possible.

Therefore, as the UV-curable resin of the thermal transfer recording material 3, those using a monofunctional monomer and a polyfunctional monomer in several parts by weight have a high curing speed and excellent heat melting properties. It is suitable. In this case, as the polyfunctional monomer, a monomer having a polymer structure that is not a dense crosslinked structure but is easily melted may be used.

The other composition of the thermal transfer recording material 3 in the second embodiment of the present invention, for example, the hot-melt substance and the colorant are the same as those in the first embodiment, so that the description will not be repeated. I do. Further, a device 10 for manufacturing the thermal transfer recording material 3 and the thermal transfer recording medium 1 and a method for manufacturing the same,
Alternatively, the reproducing device 18 for the thermal transfer recording medium 1 and the reproducing method thereof are the same as those in the first embodiment, so that the description will not be repeated.

Next, a second embodiment of the thermal transfer recording material 3 and the thermal transfer recording medium 1 of the present invention will be described with reference to specific examples.

In the present embodiment, a polyimide film having a thickness of 7.5 μm was used as the polymer resin film of the base material 2, and a monofunctional monomer was used as an ultraviolet-curable monomer as a main component of the thermal transfer recording material 3. There are used 60 parts by weight of 2-ethylhexyl carbitol acrylate having a glass transition temperature of -65 ° C. and 5 parts by weight of diethylene glycol diacrylate, which is a bifunctional monomer, and an acetophenone-based compound as a photoinitiator. 1
0 parts by weight, melting point of 85 ° C
10 parts by weight of oxidized microcrystalline wax, 5 parts by weight of a rosin derivative having a melting point of 75 ° C., and 10 parts by weight of carbon black as the coloring agent.

Then, in order to produce the thermal transfer recording material 3, of the above-mentioned materials constituting each component of the thermal transfer recording material 3, 2-ethylhexyl carbitol acrylate as a monofunctional monomer and diethylene glycol diacrylate as a bifunctional monomer were used. The photoinitiator is put into a beaker, and is stirred and melted by a motor stirrer equipped with a mantle heater and a slide rack. Next, the oxidized microcrystalline wax and the rosin derivative, which are the above-mentioned hot-melt substances, are added and stirred by heating to melt, and then carbon black is further added and mixed by stirring with heating for 30 minutes. This was cooled to room temperature while stirring, and then milled by a three-roll mill to produce a desired thermal transfer recording material 3.

Then, in order to form an ink ribbon as the thermal transfer recording medium 1, the thermal transfer recording material 3 prepared above was used.
Was poured into a paint pan serving as a recording material tank 13, and a 3 μm-thick polyimide film (manufactured by Ube Industries, Ltd.) having a thickness of 7.5 μm and subjected to back treatment with Cymac US350 (methyl ethyl ketone solution) using an offset gravure coating machine. The ink layer 4 is formed by coating so as to have a thickness. A fluororesin film having a thickness of 100 μm is attached to and adhered to the coated surface. Furthermore, a hot plate heated to 80 ° C. or higher, which is the melting point of the hot-melt substance, is applied to the fluororesin film surface, and 8 mw / cm ² ultraviolet rays are applied from the back side 2 a of the polyimide film by a high-pressure mercury lamp for 10 seconds. Irradiate. This irradiation caused the thermal transfer recording material 3 to undergo a polymerization reaction and cure, thereby producing an ink ribbon as the thermal transfer recording medium 1.

When this ink ribbon was mounted on a thermal transfer printer (manufactured by Star Seimitsu Co., Ltd.) of SJ-144 (resolution 400 dpi, manufactured by Star Seimitsu Co., Ltd.), recording was performed on word processor paper for thermal transfer (manufactured by Union Chemical Co., Ltd.). .5, and an image with good edge reproducibility was obtained.

Thereafter, the used ink ribbon is set in the reproducing apparatus 18 for the thermal transfer recording medium 1 shown in FIG. 3, and the thermal transfer recording material 3 is applied and irradiated with ultraviolet rays by the above-mentioned reproducing method to thereby form the ink defective portions 4a. Was played. Unwanted unreacted ink was removed with a blade or knife. This cleaning may be performed by a dry cleaning method.

When the thus reproduced ink ribbon was mounted on the thermal transfer printer and recording was performed again, the image density was 1.4, and a good edge reproduction which was comparable to the previous recorded image was obtained. Sex was obtained.

According to the above-described second embodiment of the thermal transfer recording material 3 and the thermal transfer recording medium 1 of the present invention, as the thermal transfer recording material 3, an ultraviolet curable resin obtained by adding a small amount of a polyfunctional monomer to a monofunctional monomer is used. Therefore, the thermal transfer recording material 3 having a high curing rate and excellent curability can be obtained, and the thermal transfer recording medium 1 excellent in heat fusibility, which can be easily melted by the calorific value of the thermal head, can be formed.

Further, the ink layer of the thermal transfer recording medium 1 can be easily formed, and reproduction is easy, and high-quality recording can be obtained even after reproduction.

It should be noted that the present invention is not limited to the above embodiments, but can be variously modified as needed.

For example, the monofunctional acrylic monomer and the monofunctional methacrylic monomer are not limited to the monomers described in the above embodiment, but may be any acrylic or methacrylic monomer having a glass transition temperature of 0 ° C. or less.

Further, the polyfunctional monomer is not limited to the monomer described in the above embodiment, and any polymer may be used as long as it is not a dense crosslinked structure and has excellent heat melting property.

Further, the melting point of the hot-melt substance is about 5
It is not necessary to limit to the embodiment as long as it is a hot-melt substance in the range of 0 to 100 ° C. and excellent in dispersibility and compatibility with the monomer.

[0155]

As described above, according to the thermal transfer recording material and the thermal transfer recording medium of the present invention, the thermal transfer recording medium capable of performing good recording can be formed by a simple method of merely irradiating ultraviolet light. Can be played. Therefore, it is possible to reduce power consumption and cost required for forming the thermal transfer recording medium.

Further, it is possible to obtain a high quality recording with a high curing rate of the thermal transfer recording material.

[Brief description of the drawings]

FIG. 1 is a side sectional view showing an embodiment of a thermal transfer recording medium according to the present invention.

FIG. 2 is an explanatory view showing the inside of a thermal transfer recording medium manufacturing apparatus according to the present invention.

FIG. 3 is an explanatory diagram showing the inside of a reproducing apparatus for a thermal transfer recording medium according to the present invention.

FIG. 4 is an explanatory view showing a method of reproducing a thermal transfer recording medium according to the present invention.

FIG. 5 is a side sectional view showing a conventional thermal transfer recording medium.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermal transfer recording medium 2 Substrate 3 Thermal transfer recording material 4 Ink layer 5 Lubricant layer 10 Manufacturing device 13 Heatable recording material tank 15 Film thickness control device 16 Ultraviolet irradiator 18 Reproducing device 23 Traveling unit

Claims (10)

[Claims] 1. A thermal transfer recording material for forming an ink layer of a thermal transfer recording medium, comprising a monofunctional monomer which undergoes radical polymerization by light and has a glass transition temperature of the polymer at or below a recordable temperature. A thermal transfer recording material comprising at least a heat melting substance having a melting point or softening point within a temperature range, and a coloring agent. 2. The compounding amount of the monofunctional monomer is 10 to 8
2. The thermal transfer recording material according to claim 1, wherein 0 parts by weight, the blending amount of the hot-melt substance is 10 to 80 parts by weight, and the blending amount of the coloring material is 1 to 25 parts by weight. 3. The thermal transfer recording material according to claim 1, wherein the monofunctional monomer is a monofunctional acrylic monomer or a monofunctional methacrylic monomer. 4. A thermal transfer recording material for forming an ink layer of a thermal transfer recording medium, comprising: a monofunctional monomer which undergoes radical polymerization by light and has a glass transition temperature of the polymer at or below a recordable temperature; A thermal transfer recording material comprising at least a polyfunctional monomer to be polymerized, a hot-melt substance having a melting point or softening point within a recordable temperature range, and a coloring agent. 5. The compounding amount of the monofunctional monomer is 10 to 8
0 parts by weight, and the compounding amount of the polyfunctional monomer is 1 to 50.
5. The thermal transfer recording material according to claim 4, wherein the amount of the hot-melt substance is 10 to 80 parts by weight, and the amount of the coloring material is 1 to 25 parts by weight. 6. 6. The monofunctional monomer and the polyfunctional monomer are an acrylic monomer or a methacrylic monomer, respectively.
2. The thermal transfer recording material according to item 1. 7. The thermal transfer recording material according to claim 1, wherein the monofunctional monomer has a polymer having a glass transition temperature of 0 ° C. or lower. 8. The heat-meltable substance contains at least one of a wax and a heat-meltable resin whose melting point or softening point is in a temperature range of 50 ° C. or more and 100 ° C. or less. The thermal transfer recording material according to claim 1. 9. The method according to claim 1, wherein the heat-fusible substance contains at least one of a wax and a heat-fusible resin having a property of being uniformly dispersed or compatible with the monofunctional monomer. The thermal transfer recording material according to any one of claims 1 to 8. 10. A thermal transfer recording medium in which an ink layer is laminated on a film substrate, wherein the ink layer comprises
A monofunctional monomer or a polyfunctional monomer of the thermal transfer recording material according to any one of claims 9 to 9, wherein the monofunctional monomer and the polyfunctional monomer are radically polymerized by light to form a polymer. A thermal transfer recording medium, comprising: