JP3160192B2 - Thermal transfer recording medium and method of manufacturing the same - Google Patents

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 medium in a thermal transfer printer used as an output terminal of an information processing apparatus such as a word processor and a facsimile, and a method of manufacturing the same. The present invention relates to a formed thermal transfer recording medium and a method for manufacturing the same.

[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, etc., and recording methods thereof include a thermal transfer method, an electrophotographic method, an ink jet method, and a wire dot method. Various methods have been proposed.

[0003] Among these, silence, low cost,
From the viewpoint of miniaturization adaptability, simple operability, and high reliability, a thermal transfer method using a heating resistor element array called a thermal head has been more widely used than in the past. It is expanding to youth and even hobby.

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 thermal paper can be roughly classified into two types, a sublimation thermal transfer system in which color is generated by the heat of a thermal head. However, at present, the fusion thermal transfer recording system is mainly used in terms of cost.

FIG. 3 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 the 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 heat-fusible resin having good adhesion between a heat-fusible substance such as a low-melting wax and recording paper, and various pigments and various kinds of colorants are used as colorants. It is constituted by adding trace amounts of a plasticizer, a dispersant, an antioxidant and the like. As the low melting point wax used for the ink layer 7, carnauba wax,
Candelilla wax, rice wax, paraffin wax, microcrystalline wax, polyethylene wax and the like can be mentioned, and these can be used alone or in combination.

The heat-meltable resin used for the ink layer 7 includes ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl butyrate copolymer, ethylene-acrylic copolymer, and polylauryl. Examples include poly (meth) acrylates such as methacrylate and polyhexyl acrylate, and vinyl chloride copolymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl alcohol copolymer. Can,
These resins are used alone or in combination.

When the thermal transfer recording medium 1 is manufactured, a hot-melt method, that is, an ink containing a heat-fusible substance such as the low-melting wax and the heat-fusible resin as main components is melted by heating. After being applied to the substrate 2 in a state,
The ink layer 7 is formed by cooling and solidifying, or the solvent is formed by immersing the base material 2 in a resin solution or its dispersion and evaporating and removing the solvent to leave an adhered film. Layer 7 was formed.

[0011]

However, when the conventional thermal transfer recording medium 1 is manufactured by the hot melt method, it is necessary to melt the ink at all times, and the apparatus becomes large and the power consumption increases. There was a problem that On the other hand, when manufacturing 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.

However, even when the thermal transfer recording medium 1 is manufactured by applying a general one of the ultraviolet curable resins to the base material 2, the glass transfer temperature, that is, the state of the viscous range or the elastic range, is hard. Since the temperature at which the state changes to the crystalline region is high in many cases, the printing obtained by the thermal transfer recording medium 1 has a problem that when the glass transition temperature is high, printing cannot be performed at all while the ink layer 7 is in a cured state. there were.

[0015] Of the ultraviolet curable resins, acrylic monomers, in particular, are inexpensive, rich in variety, and have a high polymerization rate, so that their utilization is extremely high.

However, this acrylic monomer is susceptible to the effect of inhibiting the curing of oxygen, that is, the radicals that grow the radical polymerization reaction are consumed by oxygen and cannot be sufficiently cured even when irradiated with light in the air. The surface tack (stickiness) increases. When printing is performed using the thermal transfer recording medium 1 made of only an acrylic monomer manufactured in such a state, slippage may occur during transportation due to tackiness, and ink smearing may occur. Therefore, when the thermal transfer recording medium 1 is manufactured by applying the acrylic monomer to the base material 2 and subjecting it to radical polymerization with light, a mechanism for irradiating light in an anaerobic atmosphere state or an inert atmosphere state is provided. It was necessary separately. Furthermore, even when the thermal transfer recording medium 1 manufactured in this manner is used for printing on rough paper or the like with high power, tackiness is increased and stains may occur.

The present invention has been made in view of the above problems, and does not require a mechanism for maintaining an anaerobic atmosphere state or the like, and can be easily manufactured by simply irradiating light, and good printing can be obtained. It is an object of the present invention to provide a thermal transfer recording medium and a method for manufacturing the same.

[0018]

According to a first aspect of the present invention, there is provided a thermal transfer recording medium characterized by radical polymerization by light and a polymer having a glass transition temperature of 0 ° C. or lower. The ink layer is composed of a polymer obtained by irradiating light to a photopolymerizable monomer obtained by mixing an acrylic monomer and a monomer that can be ionically polymerized by light. By employing such a configuration, an ink layer can be formed only by irradiating light, and a thermal transfer recording medium capable of performing good printing can be obtained.

The feature of the thermal transfer recording medium according to the second aspect is that the blending amount of the acrylic monomer according to the first embodiment is 10 to 80 parts by weight, and the blending amount of the monomer which can be ionically polymerized by light is adjusted. 1 to 35 parts by weight, the compounding amount of the hot-melt substance is 10 to 80 parts by weight, and the compounding amount of the coloring material is 1 to 25 parts by weight. By adopting such a configuration, it is possible to easily manufacture a thermal transfer recording medium capable of more reliably performing good printing.

A feature of the thermal transfer recording medium according to claim 3 is that the monomer capable of being ion-polymerized by light according to claim 1 or 2 is a vinyl ether monomer or an epoxy monomer. By adopting such a configuration, it is possible to easily manufacture a thermal transfer recording medium capable of more reliably performing good printing.

A feature of the thermal transfer recording medium according to the present invention is that the thermal transfer recording medium is characterized by radical polymerization by light and an acrylic monomer having a glass transition temperature of 0.degree. -The ink layer is composed of a polymer obtained by irradiating light to a photopolymerizable monomer mixed with a thiol-based monomer. By employing such a configuration, an ink layer can be formed only by irradiating light, and a thermal transfer recording medium capable of performing good printing can be obtained.

A feature of the thermal transfer recording medium according to the present invention is that the blending amount of the acrylic monomer is 10 to 80.
Parts by weight, the compounding amount of the ene / thiol monomer is 1 to 35 parts by weight, and the compounding amount of the hot-melt substance is 10 to 10 parts by weight.
80 parts by weight, and the blending amount of the coloring material is 1 to 25 parts by weight. By adopting such a configuration, it is possible to easily manufacture a thermal transfer recording medium capable of more reliably performing good printing.

According to a sixth aspect of the present invention, there is provided a method for manufacturing a thermal transfer recording medium, wherein when irradiating a recording material containing a photopolymerizable monomer having two different properties with light, the temperature of the recording material is changed to a heat melting material. The melting point or the softening point. By adopting such a configuration, the polymerization reaction can easily proceed when the two types of photopolymerizable monomers are well mixed and irradiated with light.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to an embodiment shown in the drawings.

First, a first embodiment of the thermal transfer recording medium 1 of the present invention will be described with reference to FIG.

As shown in FIG. 1, the thermal transfer recording medium 1 of the present invention has a configuration in which an ink layer 4 obtained by curing a thermal transfer recording material 3 is laminated on a substrate 2.
A lubricating layer 5 is formed on the back surface 2a of the substrate. The thermal transfer recording material 3 constituting the ink layer 4 is mainly composed of an ultraviolet curable resin which is cured by irradiating ultraviolet rays as light, and contains a heat melting substance, a coloring agent, and other trace additives as necessary. The composition is about 0 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 recording material for thermal transfer 3 will be described.

First, the general UV-curable resin includes 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.

Further, the photoinitiator absorbs ultraviolet rays to trigger a polymerization reaction.

Among the general UV-curable resins having the above-mentioned structure, the UV-curable resin in the first embodiment is particularly one which plays the role of the photopolymerizable monomer and the photopolymerizable prepolymer. An acrylic monomer that undergoes a radical polymerization reaction when irradiated with ultraviolet light, and has a glass transition temperature of 0 ° C. or lower, and an epoxy monomer that performs an ionic polymerization reaction when irradiated with ultraviolet light Alternatively, a photopolymerizable monomer obtained by mixing both with a vinyl ether-based monomer is used.

The amount of these monomers in the recording material for thermal transfer 3 is 10 to 80 parts by weight, preferably 20 to 70 parts by weight for the acrylic monomer. Alternatively, the amount of the vinyl ether monomer is 1 to 35 parts by weight, preferably 5 to 25 parts by weight. If the compounding amount of the acrylic monomer is 10 parts by weight or less, the coating material viscosity at room temperature becomes high and coating cannot be performed,
When the amount is more than 80 parts by weight, the thermal transferability is inferior. This acrylic monomer is generally available at low cost and is superior to other monomers in that it has a high polymerization rate (curing rate).

The acrylic monomer used in the first embodiment has a glass transition temperature of 0 ° C. or lower of a polymer formed by radical polymerization. The glass transition temperature, as described above, refers to the temperature at which the state changes from a viscous region or an elastic region to a hard amorphous region, and this temperature is determined by the blending ratio of the ultraviolet curing composition, the curing temperature, and the like. Temperature. An acrylic monomer having a glass transition temperature of 0 ° C. or less of the polymer after polymerization is suitable for the ink layer 4 of the thermal transfer recording medium 1, and an acrylic monomer having a glass transition temperature of −10 ° C. or less. Monomers have been found to be more suitable. If an acrylic monomer having a glass transition temperature of 0 ° C. or higher is used, thermal transferability is inferior,
Since a wax having a low melting point must be used as the hot-melt substance, the printed state is liable to be stained or crushed.

Now, the above-mentioned radical polymerization reaction will be described. This reaction is one of ultraviolet curing reactions and requires a photoinitiator, and is usually carried out by a start reaction, a growth reaction, a chain transfer reaction and a termination reaction. Reaction. 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. In addition, as a main method of activating the photoinitiator,
There are 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.

Next, the ionic polymerization reaction of the epoxy monomer or the vinyl ether monomer among the light receiving / synthesizing monomers when receiving ultraviolet light will be described.

This ionic polymerization reaction is one of ultraviolet curing reactions, and this reaction usually uses a diazo compound as a photoinitiator in many cases. For example, a fluoroalkyl borates aryldiazonium as shown in the following Chemical Formula 1 is decomposed by ultraviolet irradiation, to produce a boron trifluoride BF _3. Then, the boron trifluoride BF ₃ causes an ionic reaction as shown in the following chemical formula 2 and reacts with the oxirane compound. Generated cation (cation)
Grows one after another by reacting with the oxirane compound, and this reaction continues until the raw materials are exhausted. Polymers formed by the above cationic polymerization,
Since there is no curing inhibition by oxygen, it has excellent surface curability and good adhesion. Further, it has characteristics such as low viscosity, low odor and irritation compared to acrylic monomers.

In addition to the epoxy monomer or the vinyl ether monomer, oxetane monomers, furan monomers, lactone monomers, oxazoline monomers, cyclic siloxane monomers, etc. There is. However, among these, the epoxy-based monomer and the vinyl ether-based monomer are easily available, have a high curing speed, and have excellent adhesion, and are suitable as thermal transfer recording materials.

In the ultraviolet curable resin according to the first embodiment, a monomer obtained by mixing an acrylic monomer for performing the radical polymerization and an epoxy or vinyl ether monomer for performing the ionic polymerization is used. Such a photopolymerizable prepolymer is not blended. This is because consideration was given to keeping the material cost as low as possible, and a desired effect can be sufficiently obtained with only the photopolymerizable monomer.

Incidentally, depending on the type of the monomer, the photopolymerizable prepolymer may be used in a small amount in order to improve the polymerization rate.

Next, among the photopolymerizable monomers used for the thermal transfer recording material 3, acrylic monomers include 2-ethylhexyl carbitol acrylate,
Phenol EO-modified acrylate, nonylphenol E
O-modified acrylates can be mentioned as preferred.

Suitable epoxy monomers include phenyl glycidyl ether and metal glycidyl ether.

Further, as the vinyl ether-based monomer, triethylene glycol divinyl ether, hydroxybutyl vinyl ether and dodecyl vinyl ether can be preferably mentioned.

The photo-initiator for activating the photo-polymerizable monomer in the first embodiment will be described. The photo-activator of the acrylic monomer usually used is biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, benzyldimethyl ketal, tetramethylthiuram sulfide, azobisisobutylnitrile, benzoyl peroxide, di-tert-
Butyl peroxide, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One, 2-chlorothioxanthone, methylbenzoylformate and the like can be mentioned as preferable ones.

On the other hand, cationic photoinitiators for activating the epoxy monomer and the vinyl ether monomer include diazonium salts, iodonium salts,
Suitable examples include sulfonium salts, metal complexes, arylsilanol / aluminum complexes, and pyridinium salts.

In the first embodiment, the amount of the acrylic monomer in the thermal transfer recording material 3 is considerably larger than the amount of the epoxy monomer or the vinyl ether monomer. As the photoactivator, one that activates an acrylic monomer may be used.

Next, among the other components of the recording material 3 for thermal transfer, a heat-fused substance will be described.

Examples of the heat-fusible substance include petroleum wax such as paraffin, vegetable wax such as carnauba and candelilla, animal wax such as beads, coal wax such as montan, and synthetic wax such as Fischer-Tropsch, or A low-molecular-weight polyethylene, a heat-meltable or softening resin such as ethylene vinyl acetate and ethylene ethyl acrylate is used, and the blending amount thereof is 10 to 80 parts by weight, preferably 10 to 80 parts by weight.
70 parts by weight. If the blending amount of the hot-melt substance is 10 parts by weight or less, the thermal transferability is poor, and if it is 80 parts by weight or more, the coating material viscosity at room temperature becomes difficult to apply, which is preferable. Absent.

Examples of the colorant include black pigments such as carbon black, acetylene black and oil black, white pigments such as titania and calcium carbonate, and known dyes such as yellow, magenta and cyan. The color tone and the like can be adjusted to a desired state by appropriately changing the amount of the pigment or 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.

Further, the trace additives include oils such as silicone oil, liquid waxes such as jojoba oil,
Examples thereof include a tackifying resin such as hydrogenated rosin and hydrogenated terpene, and a dispersant, and the compounding amount is 0 to 20 parts by weight, preferably 0 to 10 parts by weight. If the oil is 2
If it is added in an amount of 0 parts by weight or more, stains are likely to occur during printing, and if the tackifying resin is added in an amount of 20 parts by weight or more, it is not preferable because the ink is hardly removed from the substrate 2.

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

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

First, a method for producing the above-described thermal transfer recording material 3 will be described. The materials constituting the 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 a normal dispersing machine such as a three-roll mill to produce the recording material 3 for thermal transfer. During the milling, heating may be performed slightly to improve the dispersion efficiency.

Next, the recording material 3 for thermal transfer is formed at room temperature by a usual coating method such as direct gravure, knife, blade, reverse, wire bar, rod, etc., so that the base material 2 has a uniform film thickness. Apply to
During this coating, heating may be performed slightly to improve the coating efficiency.

Then, as shown in FIG. 2, the base material 2 of the thermal transfer recording medium 1 on which the thermal transfer recording material 3 is entirely coated.
The entire surface is irradiated with ultraviolet rays by the ultraviolet irradiator 6 from the side, that is, the back surface 2a side. When the ultraviolet rays reach the thermal transfer recording material 3 via the base material 2, the photopolymerizable monomer in the thermal transfer recording material 3 polymerizes, and the surface of the coated thermal transfer recording material 3 is coated. Then, the inside is hardened almost uniformly within a short time, and the ink layer 4 is formed, whereby the thermal transfer recording medium 1 is manufactured. When printing is performed using the thus-produced thermal transfer recording medium 1, the printed state shows a very good state.

Here, the light source of the ultraviolet irradiator 6 is as follows.
At least one UV-emitting device such as a low-pressure or high-pressure mercury lamp, a mercury-xenon lamp, and a metal halide lamp is used. Ultraviolet light emitted from the ultraviolet irradiator 6 is diffused light or collected through a condenser lens (not shown). Either may be used.

At the time of ultraviolet irradiation by the ultraviolet irradiator 6, the temperature of the coated thermal transfer recording material 3 is preferably set to a temperature equal to or higher than the melting point or softening point of the wax of the hot-melt substance. This is because the recording material for thermal transfer 3 is mainly composed of a photopolymerizable monomer having a property different from a monomer that undergoes radical polymerization and a monomer that undergoes ionic polymerization. This is because when the hot-melt substance, which is a resin or a softening resin, is in a liquid or softened state, it is easier to polymerize the monomers with each other than in a solid state.

When the ultraviolet ray is irradiated by the ultraviolet ray irradiator 6, the surface of the coated thermal transfer recording material 3 is kept in an anaerobic atmosphere or an inert atmosphere despite the radical polymerization of the acrylic monomer. do not have to.
This is because, when a photopolymerizable monomer obtained by mixing the acrylic monomer and the epoxy monomer is used, the ionic polymerization by the epoxy monomer is not affected by the curing inhibition effect by oxygen, so that the thermal transfer recording medium 1 The radical polymer and the ionic polymer are respectively formed on the surface of the ink layer 4 at random. Accordingly, as a result, the effect of the oxygen curing inhibition effect on the radical polymerization of the acrylic monomer is suppressed.

On the other hand, when a photopolymerizable monomer obtained by mixing the acrylic monomer and the vinyl ether monomer is used, the ionic polymerization by the vinyl ether monomer is not affected by the curing inhibition effect of oxygen, and the vinyl ether Since the monomer and the acrylic monomer undergo radical copolymerization, it is possible to suppress the formation of only the polymer of the acrylic monomer which is susceptible to the effect of inhibiting the curing of oxygen alone on the surface of the ink layer 4. Therefore, as a result, there is no influence of the effect of inhibiting the curing of oxygen on the radical polymerization of the acrylic monomer.

For this reason, in the method for manufacturing the thermal transfer recording medium 1 of the first embodiment, only the acryl-based monomer is used as the photopolymerizable monomer, and the anaerobic necessary for curing by irradiating the monomer with ultraviolet rays. A mechanism for maintaining the atmosphere state is not required.

As described above, in the first embodiment of the present invention, since the UV-curable resin is used as the thermal transfer recording material 3 constituting the thermal transfer recording medium 1, It can be easily manufactured simply by irradiating the substrate with ultraviolet light.

Further, the apparatus for manufacturing the thermal transfer recording medium 1 only needs to have an ultraviolet irradiation apparatus and does not need a large-sized apparatus, so that power consumption is small and cost can be reduced.

Further, in addition to the acrylic monomer having a high polymerization rate, an epoxy monomer or a vinyl ether monomer which undergoes ionic polymerization and is not affected by the curing inhibition by oxygen is used as the ultraviolet curable resin. When the acrylic monomer and the epoxy monomer are used as photopolymerizable monomers, when irradiated with ultraviolet light, a polymer formed by radical polymerization and a polymer formed by ionic polymerization are randomly formed on the surface of the ink layer 4. As a result, it is possible to suppress the influence of the curing inhibition effect of oxygen. On the other hand, when the acrylic monomer and the vinyl ether monomer are used as photopolymerizable monomers, when the monomer is irradiated with ultraviolet rays, the ink layer 4
A polymer is formed by radical copolymerization of an acrylic monomer and a vinyl ether monomer on the surface of
As a result, it is possible to suppress the influence of the curing inhibition effect of oxygen.

Therefore, by using the photopolymerizable monomer in the first embodiment, a high polymerization rate of the acrylic monomer can be maintained without a separate mechanism for providing an inert atmosphere or an anaerobic atmosphere. In addition, the thermal transfer recording medium 1 can be manufactured.

When irradiating the thermal transfer recording material 3 with ultraviolet rays, the thermal transfer recording material 3 is heated so that the temperature of the thermal transfer recording material 3 is higher than the melting point or the softening point of the wax as the hot-melt substance. Therefore, the monomers constituting the photopolymerizable polymer are sufficiently mixed, and the polymerization reaction can proceed in a state where polymerization is more easily performed.

Next, the second embodiment of the thermal transfer recording medium 1 of the present invention will be described.
An embodiment will be described.

Note that, of the configuration of the second embodiment, the same configuration as the configuration 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. And

The thermal transfer recording medium 1 according to the second embodiment
Is a UV curable resin which is a main composition of the composition constituting the recording material 3 for thermal transfer, performs a radical polymerization reaction when irradiated with ultraviolet light, and has a glass transition temperature of 0 as a result of the polymer. A photopolymerizable monomer is used which is a mixture of both an acrylic monomer having a temperature of not more than ℃ and a monomer of a polyene / polythiol compound (ene / thiol monomer) which undergoes a radical addition polymerization reaction when irradiated with ultraviolet light.

The amount of each of these monomers in the thermal transfer recording material 3 is 10 to 80 parts by weight, preferably 20 to 70 parts by weight for the acrylic monomer. The thiol monomer is used in an amount of 1 to 35 parts by weight, preferably 5 to 25 parts by weight. If the amount of the acrylic monomer is less than 10 parts by weight, the viscosity of the coating material at room temperature becomes higher and coating cannot be performed, and if it is more than 80 parts by weight, the thermal transferability is poor.

Here, the radical addition polymerization reaction performed by the ene / thiol monomer will be described.

In this radical addition polymerization reaction, a polymer is produced by a usual radical polymerization reaction. At this time, even if the radical is deactivated by oxygen, an active thiyl radical is regenerated. Despite the fact, the effect of oxygen is small as a result. Further, the ene / thiol-based monomer has characteristics such as good adhesiveness, relatively high sensitivity, low viscosity and easy control of the properties of the cured product.

As described above, according to the second embodiment, as described above, the endoscope having the property of suppressing the influence of oxygen is used.
A thiol-based monomer is added to and mixed with the acrylic monomer to form a photopolymerizable monomer composed of both.
Therefore, when the photopolymerizable monomer is irradiated with ultraviolet light, a polymer formed by radical polymerization of an acrylic monomer and a polymer formed by radical addition polymerization of an ene / thiol monomer are randomly formed on the surface of the ink layer 4. As a result, it is possible to suppress the influence of the oxygen curing inhibition effect, and to form the ink layer 4 suitable as the thermal transfer recording medium 1.

Next, polyenes and polythiols suitable as the ene / thiol monomer will be described.

Among these, the polyene is mainly an oligomer having an allyl compound at its terminal, and includes those based on urethane oligomers, epoxy oligomers, melamine oligomers, and the like. In addition, it is possible that diarylidenepentaerythritol type or norbonene type polyene, vinyl ether or propargyl compound, spiro orthocarbonate, diethynylbenzene or the like can be used.

As the polythiol, thioglycolates such as pentaerythritol, trimethylolpropane and ethylene glycol, mercaptopropionate and mercaptopropyl ether are mainly used.

Further, the photoinitiator of the photopolymerizable monomer will be described. Usually, benzophenone, acetophenone, acenaphthenequinone and the like are used as the photoinitiator of the ene / thiol monomer. on the other hand,
As the photoinitiator of the acrylic monomer, those mentioned in the description of the first embodiment are used. In the second embodiment, the amount of the acrylic monomer in the recording material for thermal transfer 3 is considerably larger than the amount of the ene / thiol monomer. What activates an acrylic monomer may be used.

On the other hand, as the thermal transfer recording material 3 for producing the thermal transfer recording medium 1, a composition other than the ene-thiol monomer, for example, a heat-fusible substance, a coloring material, and the like, Are the same as in the first embodiment described above, and a repeated description thereof will be omitted.

Further, the recording material 3 for thermal transfer according to the second embodiment is prepared and applied to the substrate 2, and ultraviolet rays are irradiated by the ultraviolet irradiator 6 at a temperature not lower than the melting point or the softening point of the wax as a hot-melt substance. The method of manufacturing the thermal transfer recording medium 1 by irradiating and polymerizing to form the ink layer 4 includes:
This is performed in the same manner as in the first embodiment of the present invention described above.

When printing is performed using the thermal transfer recording medium 1 manufactured as described above, the printing state shows an extremely good state.

As described above, in the second embodiment of the present invention, since the UV-curable resin is used as the thermal transfer recording material 3 of the thermal transfer recording medium 1, There is no need to provide a mechanism for providing an active atmosphere or an anaerobic atmosphere, and the device can be easily manufactured simply by irradiating ultraviolet light.

Further, the apparatus for manufacturing the thermal transfer recording medium 1 only needs to have an ultraviolet irradiation apparatus and does not need a large-sized apparatus, so that power consumption and cost can be reduced.

Further, a photopolymerizable monomer obtained by mixing the ene / thiol monomer and the acrylic monomer is used as the thermal transfer recording material 3.
On the surface of the ink layer 4 formed by irradiating the photopolymerizable monomer with ultraviolet light, a polymer formed by radical polymerization of an acrylic monomer and a polymer formed by radical addition polymerization of an ene / thiol monomer are randomly formed. Is done.
Therefore, tackiness due to radical polymerization of the acrylic monomer can be suppressed, and adverse effects such as generation of slips and stains during conveyance of the thermal transfer recording medium 1 can be avoided.

Further, when irradiating the recording material for thermal transfer 3 coated on the base material 2 with ultraviolet rays, the temperature of the recording material for thermal transfer 3 is higher than the melting point or softening point of the wax as the hot-melt substance. , The monomers constituting the photopolymerizable polymer are sufficiently mixed, and the polymerization reaction can proceed in a state in which polymerization is easier.

[0086]

EXAMPLES Next, specific examples of each embodiment of the thermal transfer recording medium 1 of the present invention will be described with reference to examples.
For comparison with these examples, the recording material for thermal transfer 3
Comparative examples of various types of thermal transfer recording media 1 manufactured with different types of are shown.

First, first to third examples of the first embodiment of the present invention will be described.

In the first to third embodiments, an epoxy-based monomer is used as the ion-polymerizable monomer among the photopolymerizable monomers.

Among them, the thermal transfer recording medium 1 in the first embodiment uses a 4 μm-thick tolerina (manufactured by Toray) as the polymer resin film of the base material 2, and the thermal transfer recording material 3 mainly comprises As a photopolymerizable monomer as a component, an acrylic monomer having a glass transition temperature of -65 is used.
C. 37 parts by weight of M-120 (manufactured by Toa Gosei) and 10 parts by weight of KR-500 (manufactured by Asahi Denka) which is an epoxy-based monomer.
8 parts by weight (manufactured by Ciba Gaiki Co., Ltd.), 25 parts by weight of Sasol A-1 (manufactured by Sasol) and 10 parts by weight of polywax 655 (manufactured by Nippon Natural Products) MA-10 as colorant
0 (manufactured by Mitsubishi Kasei) and CLEARON P-85 (manufactured by Yasuhara Chemical) as a tackifying resin.
5 parts by weight.

Then, in order to produce the recording material 3 for thermal transfer, all the materials which are the respective components of the recording material 3 for thermal transfer described above were mixed with a stirrer at a temperature of 90 ° C. for 30 minutes.
Stir and mix for minutes, then cool to room temperature. This is milled by a three-roll mill to obtain a desired recording material 3 for thermal transfer.

Next, in order to manufacture a thermal transfer ribbon as the thermal transfer recording medium 1, the recording material for thermal transfer 3 is coated on the tolerina as the base material 2 by an offset gravure machine to form a 3 μm thick coating. Forming artifacts. afterwards,
While heating the coated product to a temperature equal to or higher than the melting point or the softening point of the hot-melt substance and the tackifying resin, the coated product is irradiated with 5000 (mj / cm ² ) ultraviolet light from a high-pressure mercury lamp, Certain M-120 and KR-500
Was polymerized to form an ink layer 4 to produce a thermal transfer ribbon.

The melting point or softening point of the hot-melt substance and the tackifying resin is indicated by Sasol A
-1 is about 96.5 ° C., and the polywax 655 is 95 to
103 ° C, CLEARON P-85 is 85 ° C.
Therefore, when irradiating the recording material 3 for thermal transfer coated on the substrate 2 with ultraviolet rays, the temperature at which the recording material 3 for thermal transfer is heated to about 100 ° C. makes the polymerization reaction of the photopolymerizable monomer more difficult. It will proceed smoothly.

Then, the thermal transfer ribbon is transferred to JT-144.
When printing on word processor paper (manufactured by Union Chemical Car) for thermal transfer using a thermal transfer printer (manufactured by Star),
A good printing state could be obtained.

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

The thermal transfer recording medium 1 in the second embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −20 ° C.
33 parts by weight of -113 (manufactured by Toa Gosei), 10 parts by weight of KR-510 (manufactured by Asahi Denka) which is an epoxy monomer, and 7 parts by weight of Dirocure 1173 (manufactured by Ciba Gaiki) are used as the photoinitiator. And 30 parts by weight of Sasol A-1 (manufactured by Sasol) as the hot-melt substance;
10 parts by weight of polywax 655 (manufactured by Nippon Natural Products), 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the coloring agent, and C as a tackifying resin
5 parts by weight of LEARONP-85 (manufactured by Yasuhara Chemical) is used.

The method of manufacturing the thermal transfer recording medium 1 according to the second embodiment is similar to the method of manufacturing the first embodiment. All of the materials to be the respective components of the recording material 3 are stirred and mixed at a temperature of 90 ° C. by a stirrer for 30 minutes, and then cooled to room temperature. This is milled with a three-roll mill to obtain the desired thermal transfer recording material 3.
Get.

Next, in order to manufacture a thermal transfer ribbon as the thermal transfer recording medium 1, the thermal transfer recording material 3 is applied onto the base material 2 tolerina by an offset gravure machine to form a 3 μm thick coating. Forming artifacts. afterwards,
While heating the coated product to a temperature equal to or higher than the melting point or the softening point of the hot-melt substance and the tackifying resin, the coated product is irradiated with 5000 (mj / cm ² ) ultraviolet light from a high-pressure mercury lamp, Certain M-113 and KR-510
Were polymerized to form an ink layer 4 to produce a thermal transfer ribbon.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition could be obtained.

Next, a third example of the first embodiment of the present invention will be described.

The thermal transfer recording medium 1 in the third embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −65 ° C.
37 parts by weight of -120 (manufactured by Toa Gosei), 10 parts by weight of KR-500 (manufactured by Asahi Denka) which is an epoxy monomer, and 8 parts by weight of Dirocure 1173 (manufactured by Ciba Gaiki) are used as the photoinitiator. And 30 parts by weight of Sasol A-1 (manufactured by Sasol) as the hot-melt substance;
5 parts by weight of Evaflex 210 (manufactured by Du Pont-Mitsui Chemicals), 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the colorant, and CL as a tackifying resin
5 parts by weight of EARONP-85 (manufactured by Yasuhara Chemical) is used.

The method of manufacturing the thermal transfer recording material 3 and the method of manufacturing the thermal transfer ribbon in the third embodiment are the same as the manufacturing method and the manufacturing method described in the first embodiment, and will be described again. Is omitted.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition was obtained.

Next, fourth to sixth examples of the first embodiment of the present invention will be described.

The thermal transfer recording medium 1 in the fourth to sixth embodiments uses a vinyl ether-based monomer as a monomer for performing ionic polymerization among the photopolymerizable monomers.

Among them, the thermal transfer recording medium 1 of the fourth embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −65 ° C.
-120 (manufactured by Toa Gosei) and 10 parts by weight of DVD-3 (manufactured by ISP), which is a vinyl ether monomer, are used as the photoinitiator, and DIALOCURE 1173 is used.
8 parts by weight (manufactured by Ciba Gaiki Co., Ltd.), 25 parts by weight of Sasol A-1 (manufactured by Sasol) and 10 parts by weight of polywax 655 (manufactured by Nippon Natural Products) MA-10 as colorant
0 (manufactured by Mitsubishi Kasei) and CLEARON P-85 (manufactured by Yasuhara Chemical) as a tackifying resin.
5 parts by weight.

The method of manufacturing the recording material 3 for thermal transfer and the method of manufacturing the thermal transfer ribbon in the fourth embodiment are the same as the manufacturing method and the manufacturing method described in the first embodiment. The description will not be repeated.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition could be obtained.

Next, a fifth example of the first embodiment of the present invention will be described.

The thermal transfer recording medium 1 of the fifth embodiment uses a 4 μm-thick tolerina (manufactured by Toray) as the polymer resin film of the base material 2, and the thermal transfer recording material 3 is composed of the main component. As a photopolymerizable monomer, an acrylic monomer, M-113 having a glass transition temperature of −20 ° C.
33 parts by weight (manufactured by Toa Gosei), 10 parts by weight of DDVE (manufactured by ISP), which is a vinyl ether monomer, 7 parts by weight of Dirocure 1173 (manufactured by Ciba Gaiki) as the photoinitiator, As a molten substance,
30 parts by weight of Sasol A-1 (manufactured by Sasol) and 10 parts of polywax 655 (manufactured by Nippon Natural Products)
5 parts by weight of MA-100 (manufactured by Mitsubishi Kasei) as the colorant, and CLE as a tackifying resin.
5 parts by weight of ARON P-85 (manufactured by Yashara Chemical) is used.

The method of manufacturing the thermal transfer recording material 3 and the method of manufacturing the thermal transfer ribbon in the fifth embodiment are the same as the manufacturing method and manufacturing method described in the first embodiment. The description will not be repeated.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition could be obtained.

Next, a sixth example of the first embodiment of the present invention will be described.

The thermal transfer recording medium 1 in the sixth embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −65 ° C.
37 parts by weight of -120 (manufactured by Toa Gosei), 10 parts by weight of DVD-3 (manufactured by ISP), which is an epoxy monomer, and 8 parts by weight of Dirocure 1173 (manufactured by Ciba Gaiki) as the photoinitiator. And 30 parts by weight of Sasol A-1 (manufactured by Sasol) as the hot-melt substance;
5 parts by weight of Evaflex 210 (manufactured by Du Pont-Mitsui Chemicals), 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the colorant, and CL as a tackifying resin
5 parts by weight of EARONP-85 (manufactured by Yasuhara Chemical) is used.

The method of manufacturing the thermal transfer recording material 3 and the method of manufacturing the thermal transfer ribbon in the sixth embodiment are the same as the manufacturing method and the manufacturing method described in the first embodiment, and will be described again. Is omitted.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition could be obtained.

Next, first to third examples of the second embodiment of the present invention will be described.

The thermal transfer recording medium 1 in the first to third examples of the second embodiment uses, as the photopolymerizable monomer, an ene-thiol-based monomer which performs radical addition polymerization by light.

Among them, the thermal transfer recording medium 1 of the first embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −65 ° C.
-120 (manufactured by Toa Gosei) and 37 parts by weight of BY-330B (manufactured by Asahi Denka Co., Ltd.)
0 parts by weight, and Dirocure 11 as the photoinitiator.
73 (manufactured by Ciba Gaiki), 25 parts by weight of Sasol A-1 (manufactured by Sasol) and 10 parts by weight of polywax 655 (manufactured by Nippon Natural Products) MA-1 as the colorant
00 (manufactured by Mitsubishi Kasei) and 5 parts by weight of CLEARON P-85 (manufactured by Yasuhara Chemical) as a tackifying resin.

The method of manufacturing the recording material for thermal transfer 3 and the method of manufacturing the thermal transfer ribbon in the first example are the same as those described in the first example of the first embodiment. Therefore, a repetitive description thereof will be omitted.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition could be obtained.

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

The thermal transfer recording medium 1 of the second embodiment uses a 4 μm thick tolerina (manufactured by Toray) as the polymer resin film of the base material 2, and the thermal transfer recording material 3
As a photopolymerizable monomer as its main component, an acrylic monomer, M-113 having a glass transition temperature of −20 ° C.
33 parts by weight (manufactured by Toa Gosei) and 7 parts by weight of BY-300B (manufactured by Asahi Denka Co., Ltd.) which is an ene / thiol monomer, and 10 parts by weight of Dirocure 1173 (manufactured by Ciba Gaiki) as the photoinitiator. Used, as the hot-melt substance, 30 parts by weight of Sasol A-1 (manufactured by Sasol),
10 parts by weight of polywax 655 (manufactured by Nippon Natural Products), 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the coloring agent, and C as a tackifying resin
5 parts by weight of LEARON P-85 (manufactured by Yasuhara Chemical) is used.

The method of manufacturing the recording material for thermal transfer 3 and the method of manufacturing the thermal transfer ribbon in the second example are the same as those described in the first example of the first embodiment. Therefore, a repetitive description thereof will be omitted.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, a good printing condition was obtained.

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

The thermal transfer recording medium 1 in the third embodiment
Has a thickness of 4 μm as the polymer resin film of the base material 2.
m of Torelina (manufactured by Toray Industries, Inc.), and the recording material for thermal transfer 3 is a photopolymerizable monomer as its main component, which is an acrylic monomer having a glass transition temperature of −65 ° C.
-120 (manufactured by Toa Gosei) and 37 parts by weight of BY-330B (manufactured by Asahi Denka Co., Ltd.)
0 parts by weight, and Dirocure 11 as the photoinitiator.
73 (manufactured by Ciba Gaiki), 30 parts by weight of Sasol A-1 (manufactured by Sasol), and 5 parts by weight of Evaflex 210 (manufactured by DuPont Mitsui Chemicals) as the hot-melt substance. MA-10 as the colorant
0 (manufactured by Mitsubishi Kasei) and CLEARON P-85 (manufactured by Yasuhara Chemical) as a tackifying resin.
5 parts by weight.

The method of manufacturing the recording material 3 for thermal transfer and the method of manufacturing the thermal transfer ribbon in the third example are the same as those described in the first example of the first embodiment. Therefore, the description will not be repeated.

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a thermal transfer printer of JT-144 (manufactured by Star), a good printing condition could be obtained.

Next, Comparative Examples 1 to 5 will be described as comparisons with the above Examples.

First, Comparative Example 1 is for comparison with the thermal transfer recording medium 1 described in the first to third examples of the first embodiment. That is, Torrelina (manufactured by Toray) having a thickness of 4 μm is used as the polymer resin film of the base material 2, and the thermal transfer recording material 3 is an acrylic monomer as a photopolymerizable monomer as a main component thereof. 32 parts by weight of M-111 (manufactured by Toa Gosei) having a glass transition temperature of 17 ° C., 5 parts by weight of KR-500 (manufactured by Asahi Denka) as the epoxy-based monomer, and Dirocure 1173 (chibagaiki) as the photoinitiator. Company)
And 3 parts by weight of the heat-fusible substance, 50 parts by weight of beeswax (manufactured by Nippon Natural Products) and 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the coloring agent, and as a tackifying resin, CLEARON P-85
5 parts by weight (manufactured by Yashara Chemical).

The method for producing the recording material for thermal transfer 3 and the method for producing the thermal transfer ribbon in Comparative Example 1 are the same as those in the above-described embodiments, and therefore, will not be described again. .

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, no print was obtained. This is because the glass transition temperature of the M-111 used as the photopolymerizable monomer is 17
° C, it is considered that the thermal transferability was inferior.

Next, Comparative Example 2 will be described.

The comparative example 2 is a thermal transfer recording medium 1 described in the fourth to sixth examples of the first embodiment.
And for comparison. That is, Torrelina (manufactured by Toray) having a thickness of 4 μm is used as the polymer resin film of the base material 2, and the thermal transfer recording material 3 is an acrylic monomer as a photopolymerizable monomer as a main component thereof. 32 parts by weight of M-111 (manufactured by Toa Gosei) having a glass transition temperature of 17 ° C., 5 parts by weight of DVD-3 (manufactured by Asahi Denka) as the vinyl ether-based monomer, and Dirocure 1173 (chibagaiki) as the photoinitiator. Company)
And 3 parts by weight of the heat-fusible substance, 50 parts by weight of beeswax (manufactured by Nippon Natural Products) and 5 parts by weight of MA-100 (manufactured by Mitsubishi Chemical) as the coloring agent, and as a tackifying resin, CLEARON P-85
5 parts by weight (manufactured by Yashara Chemical).

The method of manufacturing the recording material for thermal transfer 3 and the method of manufacturing the thermal transfer ribbon in Comparative Example 2 are the same as those in the above-described embodiments, and therefore, will not be described again. .

When the thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, no print was obtained. This is considered to be due to the fact that the glass transition temperature of the M-111 used as the photopolymerizable monomer was 17 ° C., so that the thermal transferability was poor.

Next, Comparative Example 3 will be described.

In Comparative Example 3, the thermal transfer recording medium 1 described in the first to third examples of the second embodiment was used.
And for comparison. That is, Torrelina (manufactured by Toray) having a thickness of 4 μm is used as the polymer resin film of the base material 2, and the thermal transfer recording material 3 is an acrylic monomer as a photopolymerizable monomer as a main component thereof. 32 parts by weight of M-111 (manufactured by Toa Gosei) having a glass transition temperature of 17 ° C., 5 parts by weight of BY330B (manufactured by Asahi Denka) as the ene-thiol monomer, and Dirocure 1173 (chibagaiki) as the photoinitiator. 3 parts by weight), 50 parts by weight of beeswax (manufactured by Nippon Natural Products) and 5 parts by weight of MA-100 (manufactured by Mitsubishi Kasei) as the coloring agent, CLEARON P-8 as conductive resin
5 (Yasuhara Chemical) is used in an amount of 5 parts by weight.

The method for producing the recording material for thermal transfer 3 and the method for producing the thermal transfer ribbon in Comparative Example 3 are the same as those in each of the above-described embodiments, and will not be described again. .

When this thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, no print was obtained. This is considered to be due to the fact that the glass transition temperature of the M-111 used as the photopolymerizable monomer was 17 ° C., so that the thermal transferability was poor.

Next, Comparative Example 4 will be described.

In Comparative Example 4, only an acrylic monomer was used as the photopolymerizable monomer. That is,
Tolerina (manufactured by Toray Co., Ltd.) having a thickness of 4 μm is used as the polymer resin film of the base material 2, and the thermal transfer recording material 3 is used.
Is an acrylic monomer having a glass transition temperature of -65 [deg.] C. as a photopolymerizable monomer as its main component.
20 (manufactured by Toa Gosei), 45 parts by weight of Dilocure 1173 (manufactured by Ciba Gaiki) as the photoinitiator, and Sasol A-1 as the hot-melt substance.
(Manufactured by Sasol) in an amount of 30 parts by weight and polywax 655
Using 10 parts by weight (manufactured by Nippon Natural Products)
5 parts by weight of MA-100 (manufactured by Mitsubishi Kasei) was used as the coloring agent, and CLEARON P- was used as a tackifying resin.
85 (Yasuhara Chemical) is used in 5 parts by weight.

The method for producing the recording material for thermal transfer 3 and the method for producing the thermal transfer ribbon in Comparative Example 4 are the same as those in each of the above-described embodiments, and therefore, will not be described again. .

When this thermal transfer ribbon is printed on word processing paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (made by Star) thermal transfer printer, good printing can be obtained. When printing is performed on rough paper or the like, the recording portion of the thermal transfer printer generates heat with higher power than usual, so that the ink layer 4 is melted more than necessary and becomes a dirty printing state.

Next, Comparative Example 5 will be described.

In Comparative Example 5, the recording material for thermal transfer 3 was changed to SEPTER (manufactured by Dainippon Ink), which is a commercially available UV ink.

The SEPTER is stirred and mixed at room temperature with a stirrer for 30 minutes, and the mixture is milled by a three-roll mill to obtain a recording material 3 for thermal transfer in a desired state. In order to manufacture the thermal transfer ribbon which is the thermal transfer recording medium 1, the thermal transfer recording material 3 is applied to the substrate 2 which is the 4 μm thick tolerina by the offset gravure machine so as to have a thickness of 3 μm. Thus, an ink layer 4 was formed. Thereafter, a polyethylene film was superimposed on the coated product, and irradiated with ultraviolet light of 5000 (mj / cm ² ) from a high-pressure mercury lamp to be cured, thereby producing a thermal transfer ribbon.

This thermal transfer ribbon was printed on a word processor paper for thermal transfer (manufactured by Union Chemical Car) using a JT-144 (manufactured by Star) thermal transfer printer, and the printed state was observed. Did not. This is because even if ordinary UV ink is used for the ink layer 4 of the thermal transfer ribbon, it cannot be melted at a temperature about the heating of the recording unit of the thermal transfer printer.

As described above, according to each example of each embodiment of the present invention, not only the acrylic monomer but also a monomer which undergoes ionic polymerization or radical addition polymerization which is not affected by oxygen is added to the ink layer 4 of the thermal transfer ribbon. Therefore, a thermal transfer ribbon can be easily manufactured only by irradiating ultraviolet light without requiring a mechanism for maintaining an inert atmosphere or an anaerobic atmosphere.

Therefore, the apparatus for manufacturing the thermal transfer ribbon can be reduced in size, the power consumption is small, and the cost can be reduced.

Further, since the ink layer 4 of the thermal transfer ribbon is sufficiently cured without being affected by the curing inhibition effect of oxygen and the tackiness is suppressed, adverse effects such as generation of slips and stains during the transfer of the thermal transfer ribbon are prevented. Can be prevented.

Further, when irradiating the recording material for thermal transfer 3 coated on the base material 2 with ultraviolet rays, the temperature of the recording material for thermal transfer 3 is set to a temperature higher than the melting point or softening point of the heat-fusible substance. Thus, the monomers constituting the photopolymerizable polymer are sufficiently mixed, and the polymerization reaction can proceed in a state where the polymerization is more easily performed.

The present invention is not limited to the above embodiments, but can be variously modified as needed.

For example, the photopolymerizable monomer is not limited to the monomers described in each of the above embodiments and examples, but may be a monomer which undergoes a desired radical polymerization reaction, ionic polymerization reaction or radical addition polymerization reaction by ultraviolet light. Should be fine.

[0155]

As described above, according to the thermal transfer recording medium of the present invention, a thermal transfer recording medium capable of performing good printing can be manufactured by a simple method of merely irradiating ultraviolet light.

Further, since the effect of inhibiting the curing of oxygen can be suppressed, a mechanism for maintaining the state of an inert atmosphere or an anaerobic atmosphere is not required.

[0157] Therefore, it is possible to reduce power consumption and cost required for manufacturing the thermal transfer recording medium.

Further, according to the method for producing a thermal transfer recording medium of the present invention, the thermal transfer recording material 3
Is heated so that the temperature of the thermal transfer recording material 3 is equal to or higher than the melting point or softening point of the hot-melt substance, so that each monomer constituting the thermal transfer recording material 3 The polymerization reaction can proceed in a state in which mixing is sufficient and the polymerization is easier.

[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 a method for manufacturing a thermal transfer recording medium according to an embodiment of the present invention.

FIG. 3 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 Recording material for thermal transfer 4 Ink layer 5 Lubricant layer 6 Ultraviolet irradiation device

Claims (6)

(57) [Claims] 1. A thermal transfer recording medium comprising an ink layer laminated on a film substrate, wherein the ink layer is radically polymerized by light and the polymer has a glass transition temperature of 0 ° C. or lower. And a monomer that can be ionically polymerized by light, a hot-melt substance, and a colorant, wherein the two monomers of the recording material are each polymerized by light to form a polymer. Thermal transfer recording medium. 2. The compounding amount of the acrylic monomer is 10
To 80 parts by weight, the compounding amount of the monomer capable of being ion-polymerized by light is 1 to 35 parts by weight, the compounding amount of the hot-melt substance is 10 to 80 parts by weight, and the compounding amount of the coloring material is 1 to 25 parts by weight. 2. The thermal transfer recording medium according to claim 1, wherein the thermal transfer recording medium is in parts by weight. 3. The thermal transfer recording medium according to claim 1, wherein the monomer that can be ionically polymerized by light is a vinyl ether monomer or an epoxy monomer. 4. A thermal transfer recording medium comprising an ink layer laminated on a film substrate, wherein the ink layer is radically polymerized by light and the polymer has a glass transition temperature of 0 ° C. or lower. And the two monomers of the recording material containing at least an ene-thiol monomer capable of undergoing radical addition polymerization by light, a hot-melt substance, and a colorant are polymerized by light to form a polymer. A thermal transfer recording medium characterized in that: 5. The compounding amount of the acrylic monomer is 10
To 80 parts by weight, the compounding amount of the ene / thiol monomer is 1 to 35 parts by weight, the compounding amount of the hot-melt substance is 10 to 80 parts by weight, and the compounding amount of the coloring material is 1 to 25 parts by weight.
5. The thermal transfer recording medium according to claim 4, wherein the thermal transfer recording medium is in parts by weight. 6. A recording material containing at least a photopolymerizable monomer, a hot-melt substance, and a colorant is applied to a film substrate, and the recording material is kept at a temperature equal to or higher than the melting point or softening point of the hot-melt substance. A method for producing a solid-state ink layer by irradiating light while irradiating the recording material with a polymerization reaction.