JP2016159600A - Thermosensitive transfer recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosensitive transfer recording medium having a heat-resistant lubricant layer which has self-cleaning properties and is free from maintenance, has no unevenness of thermal conduction, and can be applied to a high-speed printer that is easy to be affected by thermal conduction unevenness.SOLUTION: A thermosensitive transfer recording medium 1 has a heat-resistant lubricant layer 30 formed on one surface of a base material 10, and a dye layer 20 formed on the other surface thereof. The heat-resistant lubricant layer 30 contains a binder resin formed of a thermoplastic resin or a reactant of the thermoplastic resin and polyvalent isocyanate, inorganic particles having cleavage in one direction, and organic particles. A specific area of the inorganic particles is 8-20 m/g, and the organic particles have a particle diameter in a range of 1-2 times the thickness of the heat-resistant lubricant layer, and have a Vicat softening point of 100-200°C.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermal transfer recording medium used in a thermal transfer type printer, and more particularly to a heat-resistant slip layer of the thermal transfer recording medium.

  In general, the thermal transfer recording medium is called an ink ribbon, which 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. A heat-resistant slip layer (back coat layer) is provided. Here, the thermal transfer layer is a layer of ink that 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. It is.

  Currently, among the thermal transfer systems, the sublimation transfer system can easily form full-color images with various functions of printers, so digital camera self-prints, cards such as identification cards, amusement output, etc. Widely used.

  Along with the diversification of the applications described above, the heat-resistant slipping layer can also be applied to high-speed printers that are self-cleaning and maintenance-free, have little heat conduction unevenness, and are easily affected by heat conduction unevenness. Therefore, development of a thermal transfer recording medium having such a heat-resistant slipping layer has been demanded.

  In order to solve these demands, several methods have been proposed. For example, the durability of the thermal head is obtained by containing a surfactant composed of an alkane sulfonate sodium salt as a lubricant, and further containing a filler having a Mohs hardness of 4 or less and a true specific gravity of 1.8 times or more of the binder. A heat-sensitive transfer recording medium having a heat-resistant slipping layer that is compatible with maintenance improvement and has been proposed. (Patent Document 1).

JP 2008-188968 A

  However, when a thermal transfer recording medium proposed in Patent Document 1 is used for printing with a recent high-speed printer using a sublimation transfer method, contamination of the thermal head remains, and uneven heat conduction occurs. The resulting printing unevenness was confirmed.

  Therefore, in view of the above problems, the present invention has a heat-resistant slipping layer that is self-cleaning, maintenance-free, has no heat conduction unevenness, and can be applied to high-speed printers that are easily affected by heat conduction unevenness. It is an object of the present invention to provide a thermal transfer recording medium.

In order to solve the above problems, the thermal transfer recording medium according to the present invention is a thermal transfer recording medium in which a heat-resistant slipping layer is formed on one surface of a substrate and a dye layer is formed on the other surface, respectively. The heat-resistant slipping layer contains a thermoplastic resin or a binder resin made of a reaction product of a thermoplastic resin and a polyvalent isocyanate, inorganic particles having cleavage in one direction, and organic particles. The specific surface area of the inorganic particles is 8 ˜20 m ² / g, the organic particles have a particle size in the range of 1 to 2 times the thickness of the heat resistant slipping layer, and a Vicat softening point of 100 to 200 ° C. And

  In the heat-sensitive transfer recording medium according to the present invention, the content of inorganic particles in the heat resistant slipping layer is preferably 2 to 10%.

  In the heat-sensitive transfer recording medium according to the present invention, the organic particle content in the heat-resistant slipping layer is preferably 1 to 10% by mass.

  In the thermal transfer recording medium according to the present invention, the inorganic particles preferably have a particle diameter D50 of 2 to 7 μm.

  According to the heat-sensitive transfer recording medium of the present invention, the heat-resistant slipping layer contains a thermoplastic resin or a binder made of a reaction product of a thermoplastic resin and a polyvalent isocyanate, and inorganic particles and organic particles having cleavage in one direction. By doing so, it is possible to provide a thermal transfer recording medium that has self-cleaning properties (maintenance-free), has no unevenness in heat conduction, and can be applied to a high-speed printer.

That is, the inorganic particles contained in the heat resistant slipping layer have a unidirectional cleavage, so that they are likely to become a planar powder, and the specific surface area is in the range of 8 to ²⁰ m ² / g. The contamination of the thermal head can be suppressed. Furthermore, the organic particles are softened during printing because the particle size of the organic particles is in the range of 1 to 2 times the thickness of the heat-resistant slipping layer and the Vicat softening point is 100 to 200 ° C. The contaminants that could not be removed can be entangled and removed.

1 is a cross-sectional view illustrating a schematic configuration of a thermal transfer recording medium according to an embodiment of the present 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)
As shown in FIG. 1, the thermal transfer recording medium 1 includes a base material 10, a heat resistant slipping layer 30, and a dye layer 20.

(Configuration of base material 10)
The base material 10 is required to have heat resistance and strength that are not softened and deformed by heat pressure in thermal transfer.
For this reason, as a material of the substrate 10, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide, aramid, polystyrene, and other synthetic resin films, and It is possible to use paper such as condenser paper and paraffin paper alone or as a combined composite. In view of physical properties, workability, cost, etc., among the materials described above, a polyethylene terephthalate film is preferable.

Moreover, the thickness (length in the vertical direction in FIG. 1) of the substrate 10 can be in the range of 2 μm to 50 μm in consideration of operability and workability. In particular, when handling properties such as transfer suitability and workability are taken into consideration, those of about 2 μm to 9 μm are preferable.
Further, in the base material 10, the surface on which the heat resistant slipping layer 30 is formed (the lower surface in FIG. 1) and the surface on which the dye layer 20 is formed (the upper surface in FIG. 1). It is also possible to perform an adhesion process, and either one or both of the surfaces to be subjected to the adhesion process may be performed.

As the above-mentioned 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, and the like. Two or more types can be used in combination.
In the present embodiment, as a suitable example, it is effective to improve the adhesion between the base material 10 and the dye layer 20, and a primer-treated polyethylene terephthalate film can also be used from the viewpoint of cost.

(Configuration of heat resistant slipping layer 30)
The heat-resistant slip layer 30 is a layer formed on one side of the base material 10, and is a layer that imparts slip properties with the thermal head to the thermal transfer recording medium 1. The heat resistant slipping layer 30 in the present invention contains at least a binder resin made of a thermoplastic resin or a reaction product of a thermoplastic resin and a polyvalent isocyanate, inorganic particles having cleavage in one direction, and organic particles, and the one direction. The specific surface area of the inorganic particles having cleavage is 8 to ²⁰ m ² / g, the particle size of the organic particles is in the range of 1 to 2 times the thickness of the heat-resistant slipping layer, and the Vicat softening point Is 100 to 200 ° C. The cleavage in the present invention means a property that the crystal or rock is easily cracked in a specific direction. The Vicat softening temperature conforms to JIS K7206.

  That is, in the present invention, by forming the heat-resistant slipping layer 30 as described above, it is possible to perform printing with no unevenness in heat conduction, and it is possible to remove contamination of the thermal head. . Hereinafter, the effect of the heat-resistant slip layer 30 of the present invention will be described in more detail.

  The organic particles contained in the heat resistant slipping layer 30 of the present invention have a Vicat softening point in the range of 100 to 200 ° C., so that the organic particles are softened during printing and eaten by contaminants attached to the thermal head. It can be removed. When the Vicat softening temperature exceeds 200 ° C., the softening is not sufficient. When the Vicat softening temperature is lower than 100 ° C., the softening is excessive, so that the contaminant cannot be completely removed.

  In addition, by setting the particle size D50 of the organic particles within the range of 1 to 2 times the thickness of the heat-resistant slipping layer, it is possible to bite and remove contaminants that have softened during printing and have adhered to the thermal head. It becomes. If the particle size D50 of the organic particles is less than 1 time, the effect of removing the contamination is not seen, and if it exceeds 2 times, the organic particles adhere to the thermal head side, and the attached organic particles adhere to the inorganic particles again and are removed. Therefore, it is rare but undesirable to remain attached to the thermal head.

  The organic particles are not limited as long as the Vicat softening point is in the range of 100 to 200 ° C., and can be appropriately used from organic materials such as acrylic resin, polystyrene resin, polyethylene resin, and polypropylene resin.

  Further, the organic particles are desirably 1 to 10% by mass with respect to the heat resistant slipping layer 30. When the content is in the range of 1 to 10% by mass, it is particularly preferable to obtain a sufficient cleaning property while maintaining the print image quality.

Next, inorganic particles having a cleavage in one direction will be described.
Inorganic particles having a cleavage in one direction tend to be a flat powder due to their characteristics, and as a result, contamination of the entire thermal head can be removed. However, since the effect is due to the function of scraping off the deposit, it cannot be said to be complete. By combining this with the effect of organic particles, a sufficient decontamination effect can be obtained.

  As inorganic particles having a unidirectional cleavage, there is no particular limitation as long as the unidirectional cleavage is shown, and pyrophyllite, illite, antigolite, ambrigonite, talc, kaolinite, montmorillonite, mica, etc. are necessary. It is possible to appropriately use a pulverized product.

Further, when the specific surface area of the inorganic particles exceeds 8 m ² / g, it becomes possible to suitably remove the organic matter in a softened state attached to the thermal head. On the other hand, if it exceeds 20 m ² / g, a sufficient decontamination effect cannot be obtained because the particle size tends to be small. The specific surface area conforms to the BET method. Further, by using an inorganic material generally having a higher thermal conductivity than that of the binder resin, it is possible to preferably alleviate unevenness in heat conduction due to heat absorption generated by softening of the organic particles.

  The inorganic particles having cleavage in one direction are preferably 2 to 10% by mass with respect to the heat-resistant slip layer 30. When it is in the range of 2% to 10%, it is particularly preferable to obtain a sufficient cleaning property while maintaining the print image quality.

  Moreover, it is preferable that the particle size of the inorganic particle which has a cleavage in one direction is 2-7 micrometers. When the particle size is less than 2 μm, the cleaning property tends to deteriorate, and when it exceeds 7 μm, the print image quality tends to deteriorate.

Next, the binder resin will be described.
As a binder resin comprising a thermoplastic resin or a reaction product of a thermoplastic resin and a polyvalent isocyanate, for example, polyvinyl butyral resin, polyvinyl acetoacetal resin, polyester resin, vinyl chloride-vinyl acetate copolymer, polyether resin, polybutadiene resin, Polystyrene resin, acrylic polyol, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy acrylate, nitrocellulose resin, cellulose acetate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbonate resin, and the like can be used.

  In addition, as the polyvalent isocyanate (curing agent) used for the purpose of further improving the heat resistance, for example, isocyanates such as tolylene diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, and derivatives thereof are appropriately used. It is possible.

  As described above, the heat-resistant slipping layer 30 can be formed by adjusting a coating solution containing a binder resin, inorganic particles having cleavage in one direction, and organic particles, and applying and drying the coating solution. In addition to these materials, a functional additive imparting releasability and slipperiness, a filler, a curing agent, a solvent, and the like can be blended as necessary to prepare a coating solution.

  Examples of the functional additives include animal waxes, natural waxes such as plant waxes, synthetic hydrocarbon waxes, aliphatic alcohols and acid waxes, fatty acid esters and glycerite waxes, synthetic ketone waxes, amines and amides. Synthetic wax such as wax, chlorinated hydrocarbon wax, alpha-olefin wax, higher fatty acid ester such as butyl stearate and ethyl oleate, sodium stearate, zinc stearate, calcium stearate, potassium stearate, magnesium stearate, etc. Surfactants such as higher fatty acid metal salts, long chain alkyl phosphate esters, polyoxyalkylene alkyl aryl ether phosphate esters, or polyoxyalkylene alkyl ether phosphate esters, etc. It is possible to use.

  As the filler, silica, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, or the like can be used.

The coating amount after drying of the heat resistant slipping layer 30 is suitably about 0.1 g / m ² or more and 2.0 g / m ² or less. Here, the coating amount after drying of the heat-resistant slipping layer 30 indicates the amount of solid content remaining after the coating liquid for forming the heat-resistant slipping layer 30 is applied and dried. Similarly, the coating amount of the dye layer 20 after drying indicates the amount of solid content remaining after the coating liquid is applied and dried.

(Configuration of dye layer 20)
The dye layer 20 is a layer formed on the other side of the substrate 10. For example, a coating liquid (for formation) for forming the dye layer 20 by blending a heat-transferable dye, a binder, a solvent, and the like is used. It is formed by preparing, applying and drying.

The heat transferable dye is a dye that melts, diffuses, or sublimates and transfers due to heat.
Among the heat transfer dyes, examples of the yellow component include C.I. I. Solvent Yellow 56, 16, 30, 93, 33, C.I. I. Disperse Yellow 201, 231, 33, etc. can be used.
Among the heat transfer dyes, examples of the magenta component include C.I. I. Disperse violet 26, 31, C.I. I. Disperse thread 60, C.I. I. Solvent red 19, 27, etc. can be used.
Among the heat transfer dyes, examples of the cyan component include C.I. I. Disperse blue 24,257,354, C.I. I. Solvent blue 36, 63, 266, etc. can be used.

In general, the ink dye is toned by combining the above-described dyes.
As the resin contained in the dye layer 20, any conventionally known resin binder can be used and is not particularly limited, but includes ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, and the like. Cellulosic resins, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, polyacrylamide, and other vinyl resins, polyester resins, styrene-acrylonitrile copolymer resins, phenoxy resins, and the like can be used.

Here, the mixing ratio of the dye and the resin in the dye layer 20 is preferably (dye) / (resin) = 10/100 to 300/100 on a mass basis.
This is because if the ratio of (dye) / (resin) is less than 10/100, the amount of dye is too small and the color density becomes insufficient, and a good thermal transfer image cannot be obtained. If it exceeds the above range, the solubility of the dye in the resin is extremely lowered, and therefore, when it becomes a thermal transfer recording medium, the storage stability is deteriorated and the dye may be easily precipitated.

The dye layer 20 may contain known additives such as an isocyanate compound, a silane coupling agent, a dispersant, a viscosity modifier, and a stabilizer as long as the performance is not impaired.
An appropriate coating amount of the dye layer 20 after drying is about 1.0 g / m ² . The dye layer 20 can be composed of a single layer of one color, and a plurality of dye layers 20 containing dyes having different hues are sequentially and repeatedly formed on the same surface of the same substrate 10. It is also possible to do.

In addition, a layer is provided between the base material 10 and the dye layer 20 and between the base material 10 and the heat-resistant slipping layer 30 for the purpose of imparting functionality such as improvement in adhesion and improvement in dye utilization efficiency. It is also possible.

The heat resistant slipping layer 30 and the dye layer 20 can be formed by applying and drying by a conventionally known coating method.
As a coating method, for example, a gravure coating method, a screen printing method, a spray coating method, a reverse roll coating method, or a die coating method can be used.

Hereinafter, the effects of the thermal transfer recording medium of the present invention will be verified using Examples (Examples 1 to 16 and Comparative Examples 1 to 10) with reference to FIG. In addition, when described as “parts” in the following description, unless otherwise specified, mass reference is shown. The present invention is not limited to the following examples.
The transfer material for thermal transfer used in the examples and comparative examples was prepared by the following method.

・ Production of Transferred Body A double-sided resin-coated paper having a thickness of 190 μm was used as a base material, and a heat-insulating layer coating liquid having the composition shown below was applied on one side by a die-coating method to a coating amount after drying of 8.0 g. / M ² is applied and dried to form a heat-insulating layer, and then the upper surface of the heat-insulating layer is coated with a receiving layer coating liquid having the composition shown below by a gravure coating method to give a coating amount of 4.0 g. The material to be transferred for thermal transfer was prepared by coating and drying so as to be / m ² .

・ Insulation layer coating solution Acrylic-styrene hollow particles 35.0 parts (average particle diameter 1 μm, volume hollowness 51%)
Styrene-butadiene rubber 10.0 parts Pure water 55.0 parts Dispersant
Antifoam

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

Example 1
A polyethylene terephthalate film with a single-sided easy-adhesion treatment having a thickness of 4.5 μm is used as a base material, and a coating solution-1 for forming a heat-resistant slipping layer having the composition shown below is applied to the non-adhesive-adhesion treated surface by a gravure coating method Was applied so that the coating amount after drying was 0.7 g / m ² and dried at a temperature of 100 ° C. for 1 minute to form a heat-resistant slipping layer.

-Coating solution for forming a heat resistant slipping layer-1
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK (methyl ethyl ketone) 20.0 parts Toluene 60.0 parts

Next, a dye layer coating solution having the composition shown below is applied to the surface of the base material on which the heat-resistant slip layer is formed by a gravure coating method, so that the coating amount after drying becomes 0.70 g / m ² . And dried at a temperature of 90 ° C. for 1 minute to form a dye layer to obtain a thermal transfer recording medium. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Dye layer coating solution C.I. I. Solvent Blue 63 6.0 parts Polyvinyl acetal resin 4.0 parts Toluene 45.0 parts Methyl ethyl ketone 45.0 parts

(Example 2)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer-forming coating liquid-2 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating liquid for forming a heat resistant slipping layer-2
Binder resin: Butyral resin 14.8 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 0.2 parts
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 3)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was produced using the coating solution-3 for forming a heat-resistant slipping layer having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for forming heat resistant slipping layer-3
Binder resin: Butyral resin 14.5 parts Organic particles: Polypropylene particles 1.0 part
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 0.5 parts
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

Example 4
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer forming coating solution-4 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for forming heat resistant slipping layer-4
Binder resin: Butyral resin 13.2 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.8 parts
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 5)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was produced using the heat-resistant slipping layer forming coating solution-5 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for heat resistant slipping layer formation-5
Binder resin: Butyral resin 12.8 parts Organic particles: Polypropylene particles 1.0 part
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 2.2 parts
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 6)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer forming coating solution-6 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for forming heat resistant slipping layer-6
Binder resin: Butyral resin 12.8 parts Organic particles: Polypropylene particles 1.0 part
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 2.2 parts
(Cleaving in one direction, specific surface area 15 m ² / g particle size 2.5 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 7)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was produced using the heat-resistant slipping layer forming coating solution-7 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating solution for heat-resistant slip layer-7
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 19 m ² / g particle size 1.5 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 8)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was produced using the heat-resistant slipping layer forming coating solution-8 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for heat resistant slipping layer formation-8
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 9 m ² / g particle size 6.5 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

Example 9
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was produced using the heat-resistant slipping layer forming coating solution-9 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for heat resistant slipping layer formation-9
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.2 m ² / g particle size 7.3 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 10)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was produced using the heat-resistant slip layer forming coating solution-10 having the following composition. The particle size of the organic particles was 1.71 times the coating amount of the heat resistant slipping layer.

・ Coating solution for forming heat resistant slipping layer-10
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 11)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer-forming coating liquid 11 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating solution for heat resistant slipping layer formation-11
Binder resin: Butyral resin 14.8 parts Organic particles: Polypropylene particles 0.2 parts
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 12)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was prepared using the heat-resistant slipping layer forming coating solution-12 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for heat resistant slipping layer formation-12
Binder resin: Butyral resin 14.85 parts Organic particles: Polypropylene particles 0.15 parts
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 13)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer-forming coating liquid-13 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating solution for forming a heat resistant slipping layer -13
Binder resin: Butyral resin 13.1 parts Organic particles: Polypropylene particles 1.9 parts
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 14)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was prepared using the heat-resistant slipping layer forming coating solution-14 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating solution for heat resistant slipping layer formation-14
Binder resin: Butyral resin 12.9 parts Organic particles: Polypropylene particles 2.1 parts
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Example 15)
A thermal recording transfer medium was obtained in the same manner as in Example 1 except that the coating amount after drying of the heat resistant slipping layer was 0.9 g / m ² . The particle size of the organic particles was 1.11 times the coating amount of the heat resistant slipping layer.

(Example 16)
A thermal recording transfer medium was obtained in the same manner as in Example 1 except that the coating amount after drying of the heat resistant slipping layer was 0.55 g / m ² . The particle size of the organic particles was 1.82 times the coating amount of the heat resistant slipping layer.

(Comparative Example 1)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was prepared using Coating Solution-15 for forming a heat-resistant slipping layer having the following composition.

・ Coating fluid for heat-resistant slip layer-15
Binder resin: Butyral resin 15.0 parts Inorganic particles: Mica 1.0 parts
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 2)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was prepared using the heat-resistant slipping layer forming coating solution-16 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for forming heat resistant slipping layer-16
Binder resin: Butyral resin 15.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Calcite 1.0 part
(Cleaving in three directions, specific surface area 14 m ² / g particle size 3 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 3)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer forming coating solution-17 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating solution for heat-resistant slip layer-17
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Calcite 1.0 part
(Cleaving in three directions, specific surface area 14 m ² / g particle size 3 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 4)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer-forming coating liquid-18 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating liquid for forming heat-resistant slipping layer-18
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Magnesium oxide 1.0 part
(No cleavage, specific surface area 18 m ² / g particle size 2 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 5)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slipping layer was prepared using the heat-resistant slipping layer forming coating solution-19 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating liquid for heat-resistant slip layer-19
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 21 m ² / g particle size 1.5 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 6)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer forming coating solution-20 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating solution for heat resistant slipping layer formation -20
Binder resin: Butyral resin 14.0 parts Organic particles: 1.0 parts of polypropylene particles
(Vicat softening point 102 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 7 m ² / g particle size 9 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 7)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was produced using the heat-resistant slip layer forming coating liquid-21 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

-Coating liquid for heat resistant slipping layer formation-21
Binder resin: Butyral resin 14.0 parts Organic particles: Cross-linked acrylic styrene 1.0 part
(Vicat softening point 210 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 8)
A heat-sensitive recording transfer medium was obtained in the same manner as in Example 1 except that the heat-resistant slip layer was prepared using the heat-resistant slip layer forming coating liquid-22 having the following composition. The particle size of the organic particles was 1.43 times the coating amount of the heat resistant slipping layer.

・ Coating fluid for forming heat resistant slipping layer-22
Binder resin: Butyral resin 14.0 parts Organic particles: Polyethylene 1.0 part
(Vicat softening point 94 ° C grain size 1μm)
Inorganic particles: Mica 1.0 part
(Cleaving in one direction, specific surface area 8.5 m ² / g particle size 6 μm)
Functional additive: Zinc stearate 4.0 parts Solvent: MEK 20.0 parts Toluene 60.0 parts

(Comparative Example 9)
A thermal recording transfer medium was obtained in the same manner as in Example 1 except that the coating amount after drying of the heat-resistant slipping layer was 1.1 g / m ² . The particle size of the organic particles was 0.91 times the coating amount of the heat resistant slipping layer.

(Comparative Example 10)
A thermal recording transfer medium was obtained in the same manner as in Example 1 except that the coating amount after drying of the heat resistant slipping layer was 0.45 g / m ² . The particle size of the organic particles was 2.22 times the coating amount of the heat resistant slipping layer.

(Evaluation)
The thermal transfer recording media obtained in Examples 1 to 16 and Comparative Examples 1 to 10 were printed by the following thermal simulator, and the following methods were used for the printed matter and the thermal head after continuous printing. Evaluated. The results are shown in Table 1 below.

<Evaluation method>
Printing was performed for 10 km at a speed of 8 inches / sec at a voltage of 17 V and 20 V of the thermal simulator. The state of the thermal head and the printed material after 10 km printing with the obtained printed material was observed. With respect to the thermal head, the presence or absence of dirt was confirmed, and with respect to the printed matter, the presence or absence of uneven printing of the printed matter accompanying the wear of the thermal head was confirmed.
-Thermal head evaluation The thermal head was evaluated according to the following criteria. In addition, the sign “Δ” or more shown in Table 1, that is, the sign “Δ” and the sign “◯” indicate a level at which there is no practical problem.
○: No contamination of the thermal head is observed. Δ: The thermal head is slightly dirty. ×: The thermal head is clearly dirty. ・ Print evaluation The evaluation of the print is as follows. The standard was used. In addition, the sign “Δ” or more shown in Table 1, that is, the sign “Δ” and the sign “◯” indicate a level at which there is no practical problem.
○: Good with no unevenness in the printed material. △: Confirmed thin and granular unevenness in the printed material. ×: Confirmed granular unevenness in the printed material.

(Comparison result)
From the results shown in Table 1, the thermal transfer recording media of Examples 1 to 16 have no problems in practical use with respect to the adhesion of stains to the thermal head and the unevenness of the printed matter, and are self-cleaning and maintenance-free. It was confirmed that a heat-sensitive transfer recording medium having a heat-resistant slipping layer that can be applied to a high-speed printer that is free from uneven heat conduction and easily affected by uneven heat conduction can be obtained.

From the results of Examples 1 to 5, when the content of the inorganic particles having cleavage in one direction is less than 2%, the print quality is 20V when the head cleaning property is more than 10%. However, it was confirmed that the content of the inorganic particles having a cleavage in one direction was more preferably in the range of 2 to 10% because it was confirmed that the content was practically inferior.
Further, from the results of Examples 6 to 9, when the particle size of the inorganic particles having a cleavage in one direction is less than 2 μm, the image quality of the printed material is both 20 V for the head cleaning property to exceed 7 μm. In terms of conditions, although it was confirmed that the range was practically inferior, it was confirmed that the particle size of the inorganic particles having cleavage in one direction is more preferably in the range of 2 to 7 μm.

  Further, from the results of Examples 11 to 14, when the content of the organic particles is less than 1%, the print quality of the printed matter is practically 20 V when the head cleaning property is more than 10%. However, it was confirmed that the content of the organic particles was more preferably in the range of 1 to 10%.

  On the other hand, from the results of Comparative Examples 1 and 2, when no inorganic particles or organic particles are contained, sufficient head cleaning properties can be obtained even under the condition of 17 V, which is less likely to be a thermal transfer recording medium. It was confirmed that it was not possible. Moreover, when it did not have inorganic particles, unevenness due to uneven heat conduction was confirmed in the printed matter. Further, from the results of Comparative Examples 3 and 4, it was confirmed that sufficient head cleaning properties could not be obtained even when the inorganic particles had multidirectional cleavage or no cleavage.

Moreover, from the results of Examples 1 and 10 and Comparative Examples 7 and 8, when the Vicat softening temperature of the organic particles is out of the range of 100 to 200 ° C., sufficient head cleaning properties are not obtained, It was confirmed that it was necessary to be in the range of 100 to 200 ° C.

  Further, from the results of Examples 15 and 16 and Comparative Examples 9 and 10, when the particle size of the organic particles is less than 1 times the thickness of the heat-resistant slipping layer, sufficient head cleaning properties are obtained under any conditions. Is not obtained, and when it exceeds 2 times, a certain cleaning property can be confirmed under a printing condition of 17V with a small load on the thermal transfer recording medium 1, but the thermal transfer recording medium 1 can be confirmed. Since sufficient cleaning properties cannot be obtained under the condition of 20V with a large load, the particle size of the organic particles needs to be in the range of 1 to 2 times the thickness of the heat resistant slipping layer. It was confirmed.

Further, from the results of Examples 7 and 9 and Comparative Examples 5 and 6, when the specific surface area of the inorganic particles exceeds 20 m ² / g or less than 8 m ² / g, the load on the thermal transfer recording medium 1 is large 20 V. It was confirmed that the specific surface area of the inorganic particles needs to be in the range of 8 to ²⁰ m ² / g because sufficient cleaning properties cannot be obtained under the above conditions.

  The thermal transfer recording medium obtained by the present invention can be used in a sublimation transfer type printer, and 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 prints and identification cards, and amusement output.

DESCRIPTION OF SYMBOLS 1 Thermal transfer recording medium 10 Base material 20 Dye layer 30 Heat resistant slipping layer

Claims (4)

A heat-sensitive transfer recording medium in which a heat-resistant slipping layer is formed on one surface of a substrate and a dye layer is formed on the other surface,
The heat-resistant slipping layer contains a thermoplastic resin or a binder resin made of a reaction product of a thermoplastic resin and a polyvalent isocyanate, inorganic particles having cleavage in one direction, and organic particles,
The inorganic particles have a specific surface area of 8 to ²⁰ m ² / g,
The thermal transfer recording medium, wherein the organic particles have a particle size in the range of 1 to 2 times the thickness of the heat-resistant slipping layer and a Vicat softening point of 100 to 200 ° C.   2. The heat-sensitive transfer recording medium according to claim 1, wherein the content of inorganic particles in the heat-resistant slipping layer is 2 to 10%.   The thermal transfer recording medium according to claim 1 or 2, wherein the content of the organic particles in the heat resistant slipping layer is 1 to 10% by mass.   The thermal transfer recording medium according to claim 1, wherein the inorganic particles have a particle diameter D50 of 2 to 7 μm.

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