JP6237049B2 - Thermal transfer recording medium and thermal transfer printed matter - Google Patents

Description

  The present invention relates to a thermal transfer recording medium used in a thermal transfer type printer, and more particularly to a thermal transfer recording medium in which a thermal transferable protective layer is formed on a substrate so as to be peelable. Specifically, the present invention relates to a thermal transfer recording medium capable of imparting a matte tone with excellent design to an image obtained by the thermal transfer method.

  The thermal transfer recording medium is generally called a thermal ribbon, and is an ink ribbon used in a thermal transfer type printer. A thermal transfer layer is provided on one side of a substrate, and the other side of the substrate. Is provided with a heat-resistant slip layer (back coat layer). Here, the thermal transfer layer is an ink layer, and the ink is sublimated (sublimation transfer method) or melted (melt transfer method) by the heat generated in the thermal head of the printer, and transferred to the transfer target side. To do.

  Currently, among the thermal transfer systems, the sublimation transfer system can easily form full-color images with various functions of the printer, so digital camera self-prints, cards such as identification cards, amusement output, etc. Widely used. Along with the diversification of such applications, there is an increasing demand for durability to the output material obtained, and a thermal transfer recording medium having a plurality of thermal transfer layers provided on the same side of the base sheet so as not to overlap each other is provided. There is a tendency to spread.

Under such circumstances, there is an increasing demand for a thermal transfer recording medium having an improved design by providing a protective layer having a matte surface, mainly for an amusement output. As a technique related to the thermal transfer recording medium with improved design, there are techniques described in Patent Document 1 and Patent Document 2, for example.
In the technique described in Patent Document 1, the surface is made rough by roughening the surface by putting a filler in the release layer remaining on the substrate, but the filler is simply put into the release layer. In this method, the measured value of the gloss meter at 45 degrees incidence is 20 gloss, which is far from 10 gloss or less of a mat-like printed material using embossing in a normal printed material or the like.

  The technique described in Patent Document 2 is a method of roughening the surface by putting particles that expand by heat on the surface of the protective layer to be transferred, but the gloss of the surface is greatly reduced in the protective layer. If particles are introduced, the fineness and sharpness of the image are deteriorated due to the influence of the refractive index and the like, which is not preferable.

Japanese Patent No. 4142517 Japanese Patent No. 4662662

  Therefore, in view of the above problems, the present invention provides a thermal transfer recording medium that does not deteriorate the fineness or sharpness of an image while easily giving a matte tone to an image obtained by the thermal transfer method using a protective layer. For the purpose.

The thermal transfer recording medium of one embodiment of the present invention is formed on a base, a heat-resistant slipping layer formed on one side of the base , and at least a part of the other side of the base , and by thermal transfer. and the release layer remaining on the substrate, the thermal transfer recording medium comprising a protective layer formed by laminating the release layer, the release layer, the particle size at irregular is the release layer An inorganic filler having a thickness of not more than twice the thickness and an organic filler having a spherical shape and a particle size of not less than twice the thickness of the release layer are added, and the organic filler has a surface of the protective layer after transfer. It is characterized by being formed of the same resin material.

Moreover, thermal transfer recording medium according to an aspect of the present invention, the organic filler is preferably formed of a material of an acrylic resin.
In the thermal transfer recording medium according to an aspect of the present invention, a part of the organic filler added to the release layer remains in the release layer by thermal transfer, and the organic filler added to the release layer The remainder of the filler is preferably transferred to the protective layer away from the release layer by thermal transfer.
In the thermal transfer recording medium according to one embodiment of the present invention, the inorganic filler is preferably formed of a silica-based material.
In the thermal transfer recording medium according to an aspect of the present invention, the release layer preferably has a thickness in the range of 0.5 μm to 5.0 μm.

In the thermal transfer recording medium according to an aspect of the present invention, the particle size of the inorganic filler is in the range of (1/2) a or more and (9/5) a or less, where a is the thickness of the release layer. It is preferable that
In the heat-sensitive transfer recording medium according to one aspect of the present invention, the organic filler preferably has a particle size in the range of 2a to 3a, where a is the thickness of the release layer.

  The thermal transfer printed matter of one embodiment of the present invention is characterized by being printed using the above-described thermal recording medium.

  In the heat-sensitive transfer recording medium of one embodiment of the present invention, a heat-resistant slipping layer is formed on one surface of a substrate, a heat-transferable protective layer is formed on the other surface of the substrate, and the heat-transferable protective layer is It is formed by sequentially laminating a release layer and a protective layer on at least a part of the other surface of the substrate, and in the release layer, the particle size is irregular and the particle size is not more than twice the thickness of the release layer. And an inorganic filler having a spherical shape and the same resin system as the surface of the protective layer after transfer, and a particle size of at least twice the thickness of the release layer, and adding the organic filler to the protective layer after transfer It is made of the same resin material as the surface of the layer.

  As a result, the image obtained by the thermal transfer method can be stabilized, and the measured value of the gloss meter at 45 degrees incidence can be 20 gloss or less. Further, by optimizing, it is possible to provide a thermal transfer recording medium having a gloss of 10 or less.

It is a figure which shows schematic structure of the thermal transfer recording medium of embodiment of this invention.

Hereinafter, an embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described with reference to the drawings.
(overall structure)
FIG. 1 is a diagram showing a schematic configuration of the thermal transfer recording medium of this embodiment, and is a cross-sectional view of the thermal transfer recording medium as viewed from the side.
As shown in FIG. 1, the thermal transfer recording medium 1 includes a substrate 10, a heat transferable protective layer 40, and a heat resistant slipping layer 50.

(Configuration of base material 10)
The base material 10 is a member that is required to have heat resistance and strength that do not soften and deform due to heat pressure in thermal transfer.
Examples of the material of the base material 10 include polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide, aramid, polystyrene, and other synthetic resin films, and Paper such as condenser paper and paraffin paper can be used alone or as a combined composite.

In addition, as a material of the base material 10, a polyethylene terephthalate film is preferable in view of physical properties, workability, cost, and the like among the above materials.
The thickness of the substrate 10 can be in the range of 2 μm to 50 μm in consideration of operability and workability. However, when handling properties such as transfer suitability and workability are taken into consideration, it is preferable that the thickness is about 2 μm or more and 9 μm or less.

  Moreover, in the base material 10, it is also possible to perform an adhesion process on the surface on which the heat resistant slipping layer 50 and the heat transferable protective layer 40 are formed. In this case, as the adhesion treatment, it is possible to apply known techniques such as corona treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, plasma treatment, primer treatment, etc. Two or more of these treatments can be used in combination.

(Configuration of thermal transferable protective layer 40)
The heat transferable protective layer 40 is formed by sequentially laminating the release layer 20 and the protective layer 30 on the other surface (the upper surface in the drawing) of the substrate 10.
An inorganic filler 21 and an organic filler 22 are added to the release layer 20.
The inorganic filler 21 is indefinite and has a particle size that is less than or equal to twice the thickness of the release layer 20.
The organic filler 22 has a spherical shape and is formed of the same resin system as the surface of the protective layer 30 after transfer, and has a particle size that is twice or more the thickness of the release layer 20.

  Of the materials forming the release layer 20, a conventionally known resin having excellent release properties can be used as the binder resin. This includes, for example, cellulose resins, silicone resins, silicone modified resins, fluororesins, fluorine modified resins, melamine resins, polyvinyl alcohol, acrylic resins, acrylic-styrene resins, thermally crosslinkable epoxy-amino resins, and thermally crosslinkable. An alkyd-amino resin or the like can be used.

These release resins can be used alone or as a mixture. In order to improve the adhesion to the substrate, a small amount of ethylene vinyl acetate copolymer resin, polyester resin or the like can be added.
In this embodiment, as an example, the release layer 20 is formed from a binder made of the above-described resin material having releasability and two or more kinds of fillers (inorganic filler 21 and organic filler 22). A case where the surface of the mold layer 20 has fine uneven shapes having different shapes will be described.

As the inorganic filler 21, for example, known inorganic fillers such as silica, alumina, clay, talc, diatomaceous earth, zeolite, calcium carbonate, barium sulfate, zinc oxide, titania, zirconia, magnesia, and glass can be used.
The organic filler 22 is of the same resin type as the surface of the protective layer after transfer, and for example, acrylic beads, melamine beads, silicone beads, etc. can be used. Moreover, as the organic filler 22, what was hardened | cured with hardening | curing agents, such as an isocyanate type and a melamine type, can also be used.

As described above, in the inorganic filler 21 and the organic filler 22, it is possible to make the surface unevenness complex by combining the amorphous inorganic type and the spherical organic type, and to obtain an excellent mat feeling. Become.
Moreover, the inorganic filler 21 and the organic filler 22 can be used alone in each of the inorganic and organic fillers, and a plurality of kinds can be mixed and used.

In this embodiment, the relationship between the thickness of the release layer 20 and the particle size of the filler to be added is important.
In the protective layer 30, if the haze of the protective layer 30 increases while reducing the gloss of the surface, the fineness and sharpness of the image are deteriorated, which is not preferable. As long as unevenness is provided on the surface, the increase in external haze cannot be suppressed, but if the internal haze is also increased, the haze becomes too high.

For this reason, the inorganic filler 21 having a refractive index greatly different from that of the resin used on the surface of the protective layer, which can cause the internal haze to be transferred to the protective layer 30, needs to be reliably retained in the release layer 20.
On the other hand, the organic filler 22 having the same surface as the surface of the protective layer 30 is preferably used as large as possible unevenness because the internal haze is not increased even if it is transferred to the protective layer 30.

Therefore, when the thickness of the release layer 20 is a, the particle size of the inorganic filler 21 is 2a or less, preferably (1/2) a or more and (9/5) a or less, The particle size of the organic filler 22 is 2a or more, preferably 2a or more and 3a or less.
By setting it as such a particle size, since the inorganic filler 21 stays in the mold release layer 20 reliably, it becomes possible to suppress a raise of a haze. In addition to this, both the organic filler 22 stays in the release layer 20 and the one transferred to the protective layer 30 exist, and the surface irregularities can be increased.

The addition amount of the inorganic filler 21 and the organic filler 22 is 5 to 100 wt%, preferably 10 to 60 wt%, based on the binder resin, as the total amount of the two fillers.
This is because if the amount of filler added is too small, the unevenness of the surface of the release layer 20 is reduced, and the gloss of the surface of the protective layer 30 cannot be sufficiently reduced.
Moreover, when there is too much addition amount of a filler, the mold release layer 20 becomes weak, and the adhesive force with the base material 10 falls, or the retention strength of a filler falls, a filler falls off, etc. This is because problems arise.

In addition, about the mold release layer 20, in order to improve the mold release property and filler retention power, you may add a well-known hardening | curing agent represented by an isocyanate type | system | group in addition to a binder. Moreover, in order to improve mold release properties, a silicone type or fluorine type mold release agent may be added.
The thickness of the release layer 20 is preferably in the range of 0.5 μm or more and 5.0 μm or less. This is because when the release layer 20 has a thickness of 0.5 μm or less, the filler holding power decreases, and when it is 5.0 μm or more, the cohesive strength of the film decreases. This is because.

As the resin for forming the protective layer 30, any conventionally known resins having various durability and transparency can be used. Examples of this include, but are not limited to, acrylic resins, cellulose resins, polyvinyl acetal resins, and polyester resins. In particular, an acrylic resin is preferable from the viewpoint of durability and transparency.
In addition, the protective layer 30 may be configured of a plurality of layers in order to improve adhesiveness and durability. In addition, functional additives such as UV absorbers, light stabilizers, antioxidants, catalyst accelerators, colorants, gloss adjusters, fluorescent brighteners, antistatic agents can be added as needed. It is.

Here, when the protective layer 30 has a plurality of layers, an adhesive layer that comes into contact with the image receiving paper at the time of transfer is provided, but the binder resin used for the adhesive layer is not particularly limited except for the heat melting property. It is not a thing.
That is, for example, styrene resins such as polystyrene and poly α-methylstyrene, acrylic resins such as polymethyl methacrylate and polyethyl acrylate, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl Vinyl resins such as butyral and polyvinyl acetal, polyester resins, polyamide resins, epoxy resins, polyurethane resins, petroleum resins, ionomers, ethylene-acrylic acid copolymers, synthetic resins such as ethylene-acrylic acid ester copolymers, nitrocellulose Cellulose derivatives such as ethyl cellulose, cellulose acetate propionate, rosin, rosin-modified maleic resin, ester gum, polyisobutylene rubber, butyl rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, Natural resins and derivatives of synthetic rubber such as Li chlorinated olefins, it is possible to use carnauba wax, waxes such as paraffin wax.

  The thickness of the protective layer 30 is preferably in the range of 0.5 μm or more and 10.0 μm or less. This is because, when the thickness of the protective layer 30 is 0.5 μm or less, the unevenness cannot be sufficiently formed, and the mat feeling cannot be raised. When the thickness is 10.0 μm or more, the film is agglomerated. This is because the force is lowered and the transfer becomes unstable.

(Configuration of heat resistant slipping layer 50)
The heat-resistant slip layer 50 is formed on one surface of the substrate 10 (the lower surface in FIG. 1).
Further, the heat-resistant slip layer 50 can be formed using a conventionally known material. For example, a resin serving as a binder (binder resin), a functional additive that imparts releasability and slipperiness, and filling It is possible to prepare a coating solution for forming a heat-resistant slipping layer by blending an agent, a curing agent, a solvent, and the like, and apply and dry it.
The coating amount after drying of the heat resistant slipping layer 50 is suitably about 0.1 g / m ² or more and 2.0 g / m ² or less.

  Among the materials forming the heat resistant slipping layer 50, as the binder resin, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, acrylic polyol, Polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, nitrocellulose resin, cellulose acetate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, polyacrylic resin, and modified products thereof can be used. It is.

Hereinafter, materials used in the respective examples and comparative examples of the present invention will be shown.
In addition, what was described as "part" in the text is based on mass unless otherwise specified. The present invention is not limited to the following examples.
-Preparation of base material with heat-resistant slipping layer As the base material 10, a 4.5 μm polyethylene terephthalate film with a single-sided easy-adhesion treatment is used, and a heat-resistant slipping layer coating solution having the following composition is applied to the non-adhesive-adhesive surface: By applying the gravure coating method so that the film thickness after drying becomes 1.0 μm and drying at 100 ° C. for 1 minute, the base material 10 with the heat-resistant slip layer (base material with the heat-resistant slip layer) is obtained. Formed.
<Heat resistant slipping layer coating solution>
Silicon acrylate (US-350, manufactured by Toagosei Co., Ltd.) 50.0 parts Methyl ethyl ketone 50.0 parts

Example 1
The release layer coating solution-1 having the following composition was applied to the easy-adhesion treated surface of the substrate with a heat resistant slipping layer by a gravure coating method so that the film thickness after drying was 1.0 μm, at 100 ° C. The release layer 20 was formed by drying for 2 minutes.
Subsequently, a protective layer coating solution-1 having the following composition is applied on the release layer 20 by a gravure coating method so that the film thickness after drying becomes 1.5 μm, and dried at 100 ° C. for 2 minutes. Thus, the protective layer 30 was formed, and the thermal transfer recording medium of Example 1 was obtained.

<Releasing layer coating solution-1>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts <Protective layer coating solution-1 >
Acrylic resin 15.0 parts Methyl ethyl ketone 85.0 parts

(Example 2)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating liquid-2 having the following composition. Got.
<Releasing layer coating solution-2>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 0.5 part Acrylic beads (average particle size: 2.5 μm) 4.5 parts Methyl ethyl ketone 85.0 parts

(Example 3)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating liquid-3 having the following composition. Got.
<Releasing layer coating solution-3>
Acetyl cellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 1.5 μm) 4.5 parts Acrylic beads (average particle diameter: 2.5 μm) 0.5 parts Methyl ethyl ketone 85.0 parts

Example 4
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-4 having the following composition, and the thermal recording transfer medium of Example 4 was used. Got.
<Releasing layer coating solution-4>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 1.5 μm) 0.25 parts Acrylic beads (average particle diameter: 2.5 μm) 0.25 parts Methyl ethyl ketone 95.0 parts

(Example 5)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-5 having the following composition. Got.
<Releasing layer coating solution-5>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 5.0 parts Acrylic beads (average particle size: 2.5 μm) 5.0 parts Methyl ethyl ketone 80.0 parts

(Example 6)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-6 having the following composition. Got.
<Releasing layer coating solution-6>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 2.5 parts Acrylic beads (average particle size: 2.0 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 7)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-7 having the following composition, and the thermal recording transfer medium of Example 7 was used. Got.
<Releasing layer coating solution-7>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 2.5 parts Acrylic beads (average particle size: 3.0 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 8)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-8 having the following composition. Got.
<Releasing layer coating solution-8>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 0.5 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

Example 9
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating liquid-9 having the following composition. Got.
<Releasing layer coating solution-9>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.8 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 10)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-10 having the following composition. Got.
<Releasing layer coating solution-10>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 2.0 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 11)
Example 1 except that in the heat-sensitive transfer recording medium produced in Example 1, the release layer 20 was changed to a release layer coating solution-11 having the following composition, and the film thickness after drying was 0.5 μm. A thermal recording transfer medium of Example 11 was obtained using the same procedure as described above.
<Releasing layer coating solution-11>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 0.5 μm) 2.5 parts Acrylic beads (average particle diameter: 1.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 12)
Example 1 except that in the heat-sensitive transfer recording medium produced in Example 1, the release layer 20 was changed to a release layer coating solution-12 having the following composition and applied so that the film thickness after drying was 5.0 μm. A thermal recording transfer medium of Example 12 was obtained using the same procedure as described above.
<Releasing layer coating solution-12>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 8.0 μm) 2.5 parts Acrylic beads (average particle size: 13.0 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 13)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-13 having the following composition. Got.
<Releasing layer coating solution-13>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 0.20 parts Acrylic beads (average particle size: 2.5 μm) 0.20 parts Methyl ethyl ketone 89.6 parts

(Example 14)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution -14 having the following composition. Got.
<Releasing layer coating solution-14>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 5.5 parts Acrylic beads (average particle size: 2.5 μm) 5.5 parts Methyl ethyl ketone 79.0 parts

(Example 15)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-15 having the following composition. Got.
<Releasing layer coating solution-15>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 1.5 μm) 2.5 parts Acrylic beads (average particle diameter: 3.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 16)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-16 having the following composition, and the thermal recording transfer medium of Example 16 was used. Got.
<Releasing layer coating solution-16>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 0.3 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 17)
Example 1 except that in the heat-sensitive transfer recording medium prepared in Example 1, the release layer 20 was changed to a release layer coating liquid-17 having the following composition and applied so that the film thickness after drying was 0.3 μm. A thermal recording transfer medium of Example 17 was obtained using the same procedure as described above.
<Releasing layer coating solution-17>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 0.5 μm) 2.5 parts Acrylic beads (average particle diameter: 0.8 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 18)
Example 1 except that in the heat-sensitive transfer recording medium produced in Example 1, the release layer 20 was changed to a release layer coating liquid-18 having the following composition and applied so that the film thickness after drying was 6.0 μm. A thermal recording transfer medium of Example 18 was obtained using the same procedure as described above.
<Releasing layer coating solution-18>
Acetyl cellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 10.0 μm) 2.5 parts Acrylic beads (average particle diameter: 15.0 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 19)
In the heat-sensitive transfer recording medium produced in Example 1, Example 1 was used except that the release layer 20 was a release layer coating liquid-19 having the following composition and the protective layer 30 was a protective layer coating liquid-2 having the following composition. A thermal recording transfer medium of Example 19 was obtained using the same procedure.
<Releasing layer coating solution-19>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 2.5 parts Melamine beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts <Protective layer coating solution-2 >
Melamine resin 15.0 parts Methyl ethyl ketone 55.0 parts Toluene 30.0 parts

(Example 20)
In the heat-sensitive transfer recording medium produced in Example 1, Example 1 was used except that the release layer 20 was a release layer coating solution-20 having the following composition and the protective layer 30 was a protective layer coating solution-3 having the following composition. A thermal recording transfer medium of Example 20 was obtained using the same procedure.
<Releasing layer coating solution-20>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 1.5 μm) 2.5 parts Silicone beads (average particle diameter: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts <Protective layer coating solution-3 >
Silicone resin 15.0 parts Toluene 85.0 parts

(Example 21)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating liquid-21 having the following composition. Got.
<Releasing layer coating solution-21>
Acetylcellulose resin 10.0 parts Alumina filler (average particle size: 1.5 μm) 2.5 parts Silicone beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Example 22)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-22 having the following composition. Got.
<Releasing layer coating solution-22>
Acetyl cellulose resin 10.0 parts Titania filler (average particle size: 1.5 μm) 2.5 parts Silicone beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Comparative Example 1)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-23 having the following composition, and the thermal recording transfer medium of Comparative Example 1 was used. Got.
<Releasing layer coating solution-23>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 5.0 parts Methyl ethyl ketone 85.0 parts

(Comparative Example 2)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used, except that the release layer 20 was a release layer coating solution-24 having the following composition, and the thermal recording transfer medium of Comparative Example 2 was used. Got.
<Releasing layer coating solution-24>
Acetyl cellulose resin 10.0 parts Acrylic beads (average particle size: 2.5 μm) 5.0 parts Methyl ethyl ketone 85.0 parts

(Comparative Example 3)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution-25 having the following composition, and the thermal recording transfer medium of Comparative Example 3 was used. Got.
<Releasing layer coating solution-25>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle diameter: 1.5 μm) 2.5 parts Acrylic beads (average particle diameter: 1.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Comparative Example 4)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating solution -26 having the following composition, and the thermal recording transfer medium of Comparative Example 4 was used. Got.
<Releasing layer coating solution-26>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 2.5 μm) 2.5 parts Acrylic beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

(Comparative Example 5)
In the thermal transfer recording medium produced in Example 1, the same procedure as in Example 1 was used except that the release layer 20 was a release layer coating liquid -27 having the following composition, and the thermal recording transfer medium of Comparative Example 5 was used. Got.
<Releasing layer coating solution-27>
Acetylcellulose resin 10.0 parts Hydrophobic silica (average particle size: 1.5 μm) 2.5 parts Silica beads (average particle size: 2.5 μm) 2.5 parts Methyl ethyl ketone 85.0 parts

・ Preparation of Transferred Material A white foamed polyethylene terephthalate film of 188 μm was used as the substrate 10, and an image-receiving layer coating solution having the following composition was applied to one surface thereof by a gravure coating method, and the film thickness after drying was 5.0 μm. By applying and drying so as to be, a transfer object for thermal transfer was produced.
<Image-receiving layer coating solution>
Vinyl chloride-vinyl acetate-vinyl alcohol copolymer 19.5 parts Amino-modified silicone oil 0.5 part Toluene 40.0 parts Methyl ethyl ketone 40.0 parts Preparation of prints Thermal transfer of Examples 1-12 and Comparative Examples 1-10 The protective layer 40 was transferred onto the image layer with a thermal printer for evaluation to produce a printed matter (thermal transfer printed matter).

(Characteristic evaluation)
Examples 1 to 12 and Comparative Examples 1 to 10 were evaluated for confirmation of the situation during printing, gloss on the surface at 45 degrees, and whitening of the image. The evaluation results are shown in Table 1.

  As shown in Table 1, in the thermal transferable protective layer 40 comprising the release layer 20 remaining on the substrate 10 and the protective layer 30 to be transferred, when the thickness of the release layer 20 is a, the release layer 20, both inorganic filler 21 having an irregular shape and a particle size of 2a or less, and organic filler 22 having a spherical shape and the same resin system as the surface of protective layer 30 after transfer and having a particle size of 2a or more are added. It was confirmed that the gloss value at 45 degrees incident was 20 or less.

Furthermore, about the particle size of both, the particle size of the inorganic filler 21 shall be in the range of (1/2) a or more and (9/5) a or less, and the particle size of the organic filler 22 shall be in the range of 2 a or more and 3 a or less. It was confirmed that a gloss of 10 or less can be secured.
Further, by setting the thickness of the release layer 20 to 0.5 μm or more, it is possible to realize a gloss of 10 or less, and by setting the thickness of the release layer 20 to 5.0 μm or less. It was confirmed that noise during printing and even slight whitening can be suppressed.

Similarly, for the amount of filler added, it is possible to achieve a gloss of 10 or less by setting the total weight of the filler to 5% or more of the resin weight, and the total weight of the filler is equal to the resin weight. It was confirmed that by setting it to 100% or less, it is possible to suppress abnormal noise during printing and even slight whitening.
On the other hand, when only one of the fillers is added to the release layer 20 or when the particle size of the organic filler 22 is not more than twice the thickness of the release layer 20, the glossiness is not sufficiently lowered. It was confirmed that a gloss of 20 or less could not be secured.

  In addition, if the organic filler 22 is made of silica different from the material of the surface of the protective layer 30, it was confirmed that the surface was whitened from the difference in refractive index between the organic filler 22 transferred to the protective layer 30 and the protective layer 30. .

  The thermal transfer recording medium obtained according to the present invention can be used in a sublimation transfer type printer. In addition to the high speed and high functionality of the printer, various images can be easily formed in full color. It can be widely used for cards such as camera self-prints, identification cards, and amusement output.

DESCRIPTION OF SYMBOLS 1 Thermal transfer recording medium 10 Base material 20 Release layer 21 Inorganic filler 22 Organic filler 30 Protective layer 40 Thermal transfer protective layer 50 Heat resistant slipping layer

Claims (8)

A base material, a heat-resistant slip layer formed on one surface of the base material, a release layer formed on at least a part of the other surface of the base material and remaining on the base material by thermal transfer, In a thermal transfer recording medium comprising a protective layer formed by laminating on a release layer ,
In the release layer, an inorganic filler having an irregular shape and a particle size of not more than twice the thickness of the release layer, and an organic filler having a spherical shape and a particle size of not less than twice the thickness of the release layer, Add,
The heat-sensitive transfer recording medium, wherein the organic filler is formed of the same resin material as the surface of the protective layer after transfer. The organic fillers, thermal transfer recording medium as claimed in claim 1, characterized in that it is formed of a material of an acrylic resin. Part of the organic filler added to the release layer remains in the release layer by thermal transfer,
3. The thermal transfer recording medium according to claim 1, wherein the remainder of the organic filler added to the release layer is transferred to the protective layer away from the release layer by thermal transfer. 4. . The thermal transfer recording medium according to any one of claims 1 to 3, wherein the inorganic filler is formed of a silica-based material. The thermal transfer recording medium according to any one of claims 1 to 4 , wherein a thickness of the release layer is in a range of 0.5 µm or more and 5.0 µm or less. The particle size of the inorganic filler, the thickness of the releasing layer as a (1/2) a higher (9/5) from claim 1, characterized in that within the range a of claim 5 The thermal transfer recording medium described in any one of them. The thermal transfer according to any one of claims 1 to 6 , wherein the particle size of the organic filler is in the range of 2a to 3a, where a is the thickness of the release layer. recoding media. A thermal transfer printed matter, which is printed using the thermal transfer recording medium according to any one of claims 1 to 7 .

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