JP6631184B2 - Thermal transfer recording medium - Google Patents

Description

  The present invention relates to a thermal transfer recording medium used for a thermal transfer type printer.

  Generally, a thermal transfer recording medium is called a thermal ribbon, and is an ink ribbon used for a thermal transfer type printer. A thermal transfer layer is provided on one surface of a base material, and a heat-resistant transfer layer is provided on the other surface of the base material. It is provided with a lubricating layer (backcoat layer). Here, the thermal transfer layer is a layer of ink, which sublimates (sublimation transfer method) or melts (melt transfer method) the ink by heat generated in the thermal head of the printer and transfers the ink to the transfer-receiving body side. is there.

  At present, among the thermal transfer methods, the sublimation transfer method is capable of easily forming full-color images of various types in conjunction with the enhancement of the functions of printers.Therefore, self-printing of digital cameras, cards such as identification cards, output materials for amusement, etc. Widely used. With the diversification of such applications, there has been a growing demand for miniaturization, higher speed, lower cost, and durability of the resulting prints. In recent years, durability has been given to prints on the same side of the base sheet. Thermal transfer recording media having a plurality of thermal transfer layers provided so as not to overlap protective layers and the like, which have been provided, have become quite popular.

  In such a situation, as the printing speed of the printer has been further increased with the diversification and spread of applications, there has been a problem that a sufficient printing density cannot be obtained with the conventional thermal transfer recording medium. Therefore, in order to increase the transfer sensitivity, attempts have been made to improve the transfer sensitivity in printing by making the thermal transfer recording medium thinner. However, when the thermal transfer recording medium is manufactured or printed, the printing wrinkles are caused by heat or pressure. Problems, such as the occurrence of cracks, and in some cases, breakage.

  Attempts have been made to increase the ratio of dye / resin (Dye / Binder) in the dye layer of the thermal transfer recording medium to improve print density and transfer sensitivity in print. Not only does the dye rise up, but also a part of the dye migrates to the heat-resistant lubricating layer of the thermal transfer recording medium during the winding state in the manufacturing process (set-off). When the color is retransferred to the dye layer or protective layer (set-off), and this contaminated layer is thermally transferred to the transfer target, the color becomes different from the specified color, or when the so-called background stain occurs and so on.

  Attempts have been made to increase the energy at the time of image formation on the printer side rather than on the thermal transfer recording medium side, but this not only increases the power consumption but also shortens the life of the thermal head of the printer, and also increases the printing time. The so-called abnormal transfer, in which the dye layer is fused to the object to be transferred and the peeling line is generated because the dye layer and the object to be transferred are not continuously separated, or the dye layer is transferred to the object to be transferred, easily occurs. .

  A method using a release agent such as a silicone compound or a fluorine compound has been proposed for preventing fusion between the dye layer and the transfer-receiving member. As one of the methods, a method of introducing these release agents to the transfer-receiving member side has been proposed. However, in recent sublimation-type thermal transfer recording systems, the rubbing resistance of a print, alcohol resistance, light resistance, and the like are considered. From the viewpoint of improving the protection resistance, a transparent resin is often laminated as a protective layer on the transferred body after printing. At this time, if the release agent is present on the transfer object, the protective layer is difficult to be transferred, which may be disadvantageous for lamination.

As another method, it has been proposed to introduce a release agent into the dye layer.
For example, in Patent Document 1, at least a sublimable dye, a binder resin, and a dye layer ink containing a release agent, the binder resin is a polyvinyl acetal resin, and the release agent is a polysiloxane and an acetal resin. And a dye layer ink characterized by being a polyether-modified silicone.

  Patent Document 2 discloses a thermal transfer recording medium containing a fluorine-containing surfactant in a dye layer.

  When printing is performed on a thermal transfer recording medium proposed in Patent Documents 1 and 2 using a recent high-speed printer of a sublimation transfer system, when a sufficient print density cannot be obtained, or when a peeling line occurs during thermal transfer. In addition, there may be other problems such as the occurrence of abnormal transfer and abnormal transfer, and a sufficiently satisfactory printed matter cannot be obtained. Further, in the above embodiment, even if the amount of the release agent added to the dye layer is increased in order to prevent the peeling line and the abnormal transfer, not only the peeling line and the abnormal transfer are not solved, but also the image bleeding and the background are not solved. Coating problems such as bubbling as stains and ink dyes occurred, and printing wrinkles occurred due to the influence of elongation of the thermal transfer recording medium due to the application of heat and pressure.

To deal with such a problem, Patent Document 3 discloses a heat-resistant lubricating oil containing a dye layer containing a release agent composed of a polyether-modified silicone oil and a perfluoroalkyl compound, and a filler having a particle diameter D50 of a film thickness or more. There has been proposed a thermal transfer recording medium having a layer and having a temperature at which an elongation percentage in the MD direction becomes 1% when heated while applying a load of 5000 N / m ² in the MD direction and becoming 1% or more at 205 ° C. or more.

  Using the thermal transfer recording medium of Patent Document 3 and performing printing with the above-described sublimation transfer type high-speed printer, the occurrence of peeling lines, abnormal transfer, and print wrinkles during thermal transfer was eliminated without blurring or background contamination of the image. Could be suppressed.

JP 2007-84670 A JP-A-7-101166 Japanese Patent Application No. 2015-028473

However, when printing was repeatedly performed on the thermal transfer recording medium of Patent Document 3, the thermal head of the printer was worn, and a situation in which the thermal head had to be replaced occurred.
Accordingly, the present invention provides a thermal transfer recording medium capable of preventing the occurrence of peeling lines, abnormal transfer, and print wrinkles during thermal transfer while suppressing abrasion of a thermal head of a printer, without causing image bleeding or background contamination. With the goal.

The present invention is to solve the above problems, the invention according to claim 1 is provided with a heat-resistant lubricating layer on one surface of the substrate, an undercoat layer on the other surface of the substrate, In a thermal transfer recording medium having a dye layer in this order,
A coefficient of kinetic friction with respect to each of SiC, Si ₃ N ₄ , and SiON at 80 ° C. or more and 160 ° C. or less of the heat-resistant lubricating layer is 0.18 or less;
The dye layer contains at least a heat transferable dye, a binder resin, and a release agent, and the release agent is composed of a polyether-modified silicone oil and a perfluoroalkyl compound. The weight ratio of the alkyl compound is 9: 1 to 6: 4, the polyether-modified silicone oil has a molecular weight of 8000 or more, and the heat-resistant lubricating layer comprises at least a binder resin and a filler. Is a heat-sensitive transfer recording medium characterized in that the particle diameter D50 is equal to or larger than the thickness of the heat-resistant lubricating layer and less than 20% by weight based on the heat-resistant lubricating layer.

The invention according to claim 2 for solving the above-mentioned problem is characterized in that the thermal transfer recording medium is loaded with a load of 5000 N / m ² per unit area of a cross section orthogonal to the MD direction of the substrate in the MD direction of the substrate. 2. The thermal transfer recording medium according to claim 1, wherein the temperature at which the elongation percentage in the MD direction becomes 1% when heated while being stretched by pulling is 205 ° C. or higher.

  The invention according to claim 3 for solving the above problem is characterized in that the content of the release agent is 0.5 to 3.0% by mass based on the binder resin of the dye layer. Item 3. A thermal transfer recording medium according to any one of Items 1 to 2.

  With the thermal transfer recording medium according to one aspect of the present invention, while suppressing abrasion of the thermal head of the printer at the time of printing, without blurring or background contamination of the image, peeling lines and abnormal transfer during thermal transfer, and printing wrinkles. Occurrence can be prevented.

FIG. 1 is a schematic sectional view illustrating a structure of a thermal transfer recording medium according to an embodiment of the present invention. FIG. 3 is a conceptual diagram illustrating an example of a printer using the thermal transfer recording medium of the present invention. FIG. 1 is a schematic cross-sectional view illustrating a structural example of a heat-resistant lubricating layer of a thermal transfer recording medium according to an embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Also, in the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the present invention. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other respects, well-known structures and devices have not been described in order to simplify the drawing.

(Thermal transfer recording medium 100)
As shown in FIG. 1, the heat-sensitive transfer recording medium 100 according to one embodiment of the present invention includes a heat-resistant lubricating layer 140 provided on one surface of a base material 110 to provide slipperiness with a thermal head. In this configuration, an undercoat layer 120 and a dye layer 130 are sequentially formed on the surface.

  As shown in FIG. 2, the thermal transfer recording medium 100 has a dye layer 130 surface of the thermal transfer recording medium 100 and an image receiving layer surface of an object to be transferred opposed to each other in a printer. Done.

At this time, if the thermal transfer recording medium 100 is deformed by the heat pressure in the thermal transfer, wrinkles are likely to be generated at the time of printing, and therefore it is preferable that the elongation when the heat pressure is applied is small. In particular, when the temperature T at which the elongation percentage becomes 1% when the sample is heated while applying a load of 5000 N / m ^{2 in} the MD direction and the elongation is 1% or more is 205 ° C. or more, wrinkles during printing hardly occur. The above-mentioned temperature T is obtained by measuring the displacement of the sample when the sample is cooled from room temperature to 0 ° C. at −5 ° C./min and then heated to 260 ° C. at 5 ° C./min using TMA / SS6100 manufactured by SII. Derived.

(Base material 110)
The base material 110 is required to have heat resistance and strength so as not to be softened and deformed by the heat pressure in thermal transfer. Therefore, as the substrate 110, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cellophane, acetate, polycarbonate, polysulfone, polyimide, polyvinyl alcohol, aromatic polyamide, aramid, a film of a synthetic resin such as polystyrene, and capacitor paper, A composite of papers such as paraffin paper alone or in combination can be used. Among these, a polyethylene terephthalate film is preferable in consideration of physical properties, workability, cost, and the like.

  In addition, in consideration of operability and workability, the base material 110 may have a thickness in a range of 2 μm or more and 50 μm or less. Even within this range, those in the range of 2 μm or more and 9 μm or less are preferable in consideration of handling properties such as transfer suitability and workability.

  Further, at least one of the surfaces on which the heat-resistant lubricating layer 140 and the undercoat layer 120 are formed on the base material 110 may be subjected to an adhesive treatment. As the bonding treatment, for example, a corona treatment, a flame treatment, an ozone treatment, an ultraviolet treatment, a radiation treatment, a surface roughening treatment, a plasma treatment, a primer treatment and the like can be applied. Further, two or more of these treatments can be used in combination. By performing this bonding process, the adhesiveness of the heat-resistant lubricating layer 140 and the undercoat layer 120 to the substrate 110 can be improved.

(Undercoat layer 120)
Next, the undercoat layer 120 is formed mainly of a binder having good adhesion to both the base material and the dye layer. Examples of the binder include a polyvinylpyrrolidone resin, a polyvinyl alcohol resin, a polyester resin, a polyurethane resin, a polyacrylic resin, a polyvinyl formal resin, an epoxy resin, a polyvinyl butyral resin, a polyamide resin, and a polyether. Resins, polystyrene resins, styrene-acrylic copolymer resins, and the like.

Coating amount after drying of the undercoat layer 120, but are not unconditionally limited, in coating amount of solid content is ^{0.02g / m 2 ~2.0g / m 2} . If this thickness is less than 0.02 g / m ^2, there is anxiety, such as abnormal transfer by omission coating of the undercoat layer, when thicker than 2.0 g / m ^2, from the thermal head to the dye layer Has a disadvantage that heat transfer is deteriorated and print density is lowered.

  Here, the application amount of the undercoat layer 120 after drying refers to the amount of solid content remaining after applying and drying the application liquid for forming the undercoat layer. In addition, the coating amount after drying of the dye layer 130 and the coating amount after drying of the heat-resistant lubricating layer 140, which will be described later, also refer to the solid content remaining after coating and drying each coating solution. .

  For the undercoat layer 120, known additives such as ultrafine particles of a colloidal inorganic pigment, an isocyanate compound, a silane coupling agent, a dispersant, a viscosity modifier, and a stabilizer can be used. As the colloidal inorganic pigment ultrafine particles, conventionally known ones such as silica (colloidal silica), alumina or alumina hydrate (alumina sol, colloidal alumina, cationic aluminum oxide or hydrate thereof, pseudoboehmite) Etc.), aluminum silicate, magnesium silicate, magnesium carbonate, magnesium oxide, titanium oxide and the like.

(Dye layer 130)
The dye layer 130 is formed by, for example, preparing a coating liquid for forming a dye layer by mixing a heat transferable dye, a binder resin, a release agent, a solvent, and the like, and applying and drying the coating liquid. The coating amount after drying of the dye layer 130 is suitably about 1.0 g / m ² . In addition, the dye layer 130
It may be composed of a single layer of one color, or a plurality of layers containing dyes having different hues may be repeatedly formed on the same surface of the same substrate in the order of the surface.

  The heat transferable dye contained in the dye layer 130 can be used as long as it is a dye that melts, diffuses, or sublimates by heat, and is not particularly limited. Among the heat transfer dyes, examples of the yellow component include Solvent Yellow 56, 16, 30, 93, 33, Disperse Yellow 201, 231, 33 and the like. Examples of the magenta component include C.I. I. Disperse Red 60, C.I. I. Disperse Violet 26, C.I. I. Solvent Red 27 or C.I. I. Solvent Red 19 and the like. As the cyan component, for example, C.I. I. Disperse Blue 354, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 36 or C.I. I. Disperse Blue 24 and the like. It is to be noted that, as a black dye, it is general to perform toning by combining the above dyes.

  Examples of the binder resin contained in the dye layer 130 include, for example, cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, and cellulose acetate, and polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl acetal. Examples thereof include vinyl resins such as pyrrolidone and polyacrylamide, polyester resins, styrene-acrylonitrile copolymer resins, and phenoxy resins, but are not particularly limited.

  Here, the mixing ratio of the dye and the binder in the dye layer 130 is preferably (dye) / (binder) = 10/100 to 300/100 on a mass basis. This is because if the ratio of (dye) / (binder) is less than 10/100, the amount of the dye is too small, the color sensitivity is insufficient, and a good thermal transfer image cannot be obtained. On the other hand, if the ratio exceeds 300/100, the solubility of the dye in the binder is extremely reduced, so that the storage stability is deteriorated when the heat-sensitive transfer recording medium is formed, and the dye tends to precipitate. It is. Further, the dye layer 130 may contain 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.

  The release agent added to the dye layer 130 is composed of a polyether-modified silicone oil and a perfluoroalkyl compound in the present invention. By adding the above two types of release agents, fusion between the dye layer and the transfer-receiving member can be efficiently prevented. The polyether-modified silicone oil and the perfluoroalkyl compound alone can prevent fusion between the dye layer and the transfer-receiving body, respectively.However, in recent high-speed sublimation transfer type printers, peeling lines and abnormal transfer occur during thermal transfer. Occurs, and satisfactory performance cannot be obtained.

  Further, even if the amount of the release agent added is increased, the release agent is present at the bleeding of the image, background stain, occurrence of bubbling as an ink dye, and the inside of the dye layer or the interface between the undercoat layer and the dye layer. As a result, print wrinkles and abnormal transfer due to a decrease in heat resistance occur.

  On the other hand, by mixing the polyether-modified silicone oil and the perfluoroalkyl compound, the release agent component can be localized on the surface of the dye layer. Fusing can be prevented.

When the polyether-modified silicone oil is compared with the perfluoroalkyl compound, the ability of the dye layer to prevent fusion between the dye layer and the transfer-receiving material is superior to that of the polyether-modified silicone oil. In addition, since it is easily present inside the dye layer as well, there is a danger that the adhesion between the undercoat layer and the dye layer is reduced. On the other hand, the perfluoroalkyl compound is inferior to polyether-modified silicone oil in preventing fusion between the dye layer and the transfer-receiving material, but is more likely to be localized on the surface of the dye layer. This is because the surface tension of the perfluoroalkyl group contained in the fluorine-based release agent is low and has a high affinity for air.
Therefore, by mixing the polyether-modified silicone oil and the perfluoroalkyl compound, it becomes possible to localize the release agent component on the surface of the dye layer with a small amount of addition.

  Examples of the silicone oil include polyether-modified polysiloxane, polyether-modified polydimethylsiloxane, polyester-modified polysiloxane, polyester-modified polydimethylsiloxane, and aralkyl-modified polymethylalkylsiloxane. Polyether-modified silicone is preferred from the viewpoint of prevention.

  This polyether-modified silicone is obtained by introducing a polyether which is a hydrophilic group into a side chain and / or a terminal in a silicone oil (polysiloxane) which is a polymer having a siloxane bond. The siloxane chain may be in any of a linear, branched, and cross-linked form. General silicone oils do not dissolve in water at all and exhibit water repellency.However, polyether-modified silicones have excellent compatibility in aqueous and non-aqueous systems. It offers a number of excellent effects that cannot be obtained.

  Further, a silicone oil modified with a different functional group into which an alkyl group, a reactive amino group, an epoxy group, or the like is introduced simultaneously with the polyether chain can also be used according to the material composition and purpose.

The polyether-modified silicone of the present invention is commercially available under a general name. For example, the following products can be used.
Shin-Etsu Silicone KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A KF-945, KF-640, KF-642, KF-643, KF-644, KF -6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, KF-6004, X-22-4952, X-22-4272, KF-6123, Toray Dow Corning SH8700, SF8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203, Momentive Performance Materials TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452. , TSF4460 (both are trade names).
A release agent having a small molecular weight is apt to be localized on the surface of the dye layer, but is liable to decrease the background stain and the storage stability of the dye.

  As the perfluoroalkyl compound of the present invention, known compounds can be used. For example, perfluoroalkyl sulfonates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts, perfluoroalkyl amino sulfonates, perfluoroalkyl sulfonates Oligomers containing alkyl groups / hydrophilic groups, oligomers containing perfluoroalkyl groups / lipophilic groups, oligomers containing perfluoroalkyl groups / (hydrophilic groups and lipophilic groups), urethanes containing perfluoroalkyl groups / lipophilic groups, perfluoro Alkyl phosphates, perfluoroalkylcarboxylates, perfluoroalkylamine compounds, perfluoroalkyl quaternary ammonium salts, perfluoroalkyl betaines, non-dissociable perfluoroalkyl compounds and the like. .

The perfluoroalkyl compound of the invention is commercially available under a generic name, and for example, the following products can be used. Examples of the fluorine-based surfactant include Megafac F-470, Megafac F-471, Megafac F-472SF, Megafac F-474, Megafac F-475, and Megafac F manufactured by Dainippon Ink and Chemicals, Inc. -177, MegaFac F-478, MegaFac F-479, MegaFac F-480SF, MegaFac F-472, MegaFac F-483, MegaFac F-484, MegaFac F-486, MegaFac F-487 , Megafac F-489, Megafac F-172D, Megafac F-178K, Megafac F-178RM, AGC Seimi Chemical Co., Ltd. Surflon S-242, S-243, S-420, S-386, S- 611, S-651, NOF CORPORATION MODIPER F206, F606, F3636, SUMITOMO SU Emu Novec Co., Ltd. TMFC-4430, FC-4432 (both the product name), but and the like, but the present invention is not particularly limited.

The release agent is preferably in the range of 0.5 to 3.0% by mass, more preferably 1.0 to 2.0% by mass, based on the binder resin of the dye layer 30. When the amount is less than 1.0% by mass, since the absolute amount of the release agent is small, fusion occurs between the dye layer 30 and the transfer target at the time of printing, and a peeling line or abnormal transfer easily occurs.
On the other hand, when the content exceeds 3.0% by mass, problems such as background staining and bleeding, abnormal transfer, bubbling as an ink dye, and precipitation of a dye are likely to occur.

  The mixing ratio between the polyether-modified silicone oil and the perfluoroalkyl compound is preferably in the range of (polyether-modified silicone oil) / (perfluoroalkyl compound) = 9/1 to 6/4, and particularly preferably 9/6. / 1 to 8/2 are preferred.

  When the ratio is less than 9/1 (when the amount of the perfluoroalkyl compound is reduced), the release agent is less likely to be localized on the surface of the dye layer, so that the dye layer is easily fused to the transfer object. When the ratio exceeds 6/4, the ratio of the polyether-modified silicone oil is reduced, so that the dye layer and the transfer-receiving body are easily fused.

  The dye layer contains the dye, the binder resin, the polyether-modified silicone oil and the perfluoroalkyl compound as essential components, and may further contain, if necessary, various additives similar to those conventionally known.

(Heat-resistant lubricating layer 140)
Next, the heat-resistant lubricating layer 140 is a layer formed on one side of the substrate 110, and is a layer that gives the thermal transfer recording medium 100 slipperiness with a thermal head. The heat-resistant lubricating layer 140 in the present invention needs to have a kinetic friction coefficient of 0.18 or less for each of SiC, Si ₃ N ₄ and SiON at 80 ° C. or more and 160 ° C. or less. Thereby, abrasion of the thermal head due to contact with the thermal transfer recording medium 100 during printing is suppressed, and the life of the thermal head is extended. On the other hand, when the dynamic friction coefficient at 80 ° C. or more and 160 ° C. or less exceeds 0.18, the life of the thermal head is shortened due to abrasion by the heat-resistant lubricating layer 140. Note that SiC, Si ₃ N ₄ , and SiON are common thermal head materials.
The coefficient of kinetic friction was determined by using a HEIDON tribo gear 14 manufactured by Shinto Kagaku Co., Ltd. and heating the SiC, Si ₃ N ₄ , and SiON to 80 ° C. or more and 160 ° C. or less with the heat-resistant lubricating layer 40 of the thermal transfer recording medium 1 Is measured at a load of 100 g and a scanning speed of 100 mm / min.

Further, it is preferable that the heat-resistant lubricating layer 140 has an effect of suppressing the elongation of the thermal transfer recording medium 100 due to heat and pressure. When the thermal transfer recording medium 100 is deformed by thermal pressure during thermal transfer, wrinkles are likely to occur during printing. Therefore, the elongation percentage in the MD direction when the sample is heated while applying a load of 5000 N / m ² in the MD direction is particularly high. It is desirable that the temperature T at which 1% is reached is 205 ° C. or higher. However, when the undercoat layer 120 and the dye layer 130 are laminated on one surface of the base material 110, the temperature T may be lower than 205 ° C. . In this case, by using the heat-resistant lubricating layer 140 that is less deformed by heat and pressure, deformation of the entire heat-sensitive transfer recording medium 1 due to heat and pressure is suppressed, and the temperature T of the heat-sensitive transfer recording medium 100 becomes 205 ° C. or more. Need to be

  The above-mentioned temperature T is obtained by measuring the displacement of the sample when the sample is cooled from room temperature to 0 ° C. at −5 ° C./min and then heated to 260 ° C. at 5 ° C./min using TMA / SS6100 manufactured by SII. Derived.

The heat-resistant lubricating layer 140 is, for example, a resin serving as a binder, a functional additive, a filler, a curing agent, a solvent and the like are appropriately mixed to prepare a coating liquid for forming a heat-resistant lubricating layer, and then coated and dried. Can be formed. Coating amount after drying of the heat-resistant lubricating layer 140, the degree 0.1 g / m ² or more 2.0 g / m ² or less is appropriate.

  To give an example of the heat-resistant lubricating layer 140, as a binder resin which is an essential component for forming a film, 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 and the like.

  Functional additives that impart lubricity to the surface of the heat-resistant lubricating layer 140 and reduce friction with the printer head include natural waxes such as animal waxes and vegetable waxes, synthetic hydrocarbon waxes, and aliphatic alcohols. And acid-based waxes, fatty acid esters and glycerite-based waxes, synthetic ketone-based waxes, amine and amide-based waxes, chlorinated hydrocarbon-based waxes, synthetic waxes such as alpha-olefin waxes, and higher fatty acids such as butyl stearate and ethyl oleate. Esters, sodium stearate, zinc laurate, zinc stearate, calcium stearate, potassium stearate, higher fatty acid metal salts such as magnesium stearate, long-chain alkyl phosphates, polyoxyalkylene alkyl aryl ether phosphates or Surfactants such as phosphoric acid esters, such as polyoxyalkylene alkyl ether phosphate and the like.

  Contrary to the above-mentioned functional additives, fillers that perform a head cleaning function by imparting friction with the printer head include talc, silica, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, kaolin, Examples include clay, silicone particles, polyethylene resin particles, polypropylene resin particles, polystyrene resin particles, polymethyl methacrylate resin particles, and polyurethane resin particles.

  Here, the filler enters between the binder resins and prevents the binder resins from approaching each other, thereby also having an effect of suppressing the elongation of the heat-resistant lubricating layer 140 when applying heat and pressure. In particular, as for the particle diameter of the filler, as shown in FIG. 3, the particle diameter D50 is preferably equal to or greater than the thickness of the binder resin or the like 141 forming the heat-resistant lubricating layer 140, and And less than 20% by weight, a high elongation suppression effect can be obtained. On the other hand, it has been found from this study that when the content is 20% by weight or more with respect to the heat-resistant lubricating layer 140, the strength of the film itself of the heat-resistant lubricating layer 140 is reduced, and the elongation percentage with respect to temperature cannot be controlled. Further, the particle diameter D50 of the filler can be measured by a particle size distribution meter.

  Examples of the curing agent that imparts strength to the heat-resistant lubricating layer 140 include tolylene diisocyanate, triphenylmethane triisocyanate, isocyanates such as tetramethylxylene diisocyanate, and derivatives thereof, but are not particularly limited. Absent.

From the above, the operation and effect according to the present embodiment will be described below.
(1) In the thermal transfer recording medium 100 according to the present embodiment, the heat-resistant lubricating layer 140 is provided on one surface of the substrate 110, and the undercoat layer 120 and the dye layer 130 are provided on the other surface of the substrate 110 in this order. The dye layer 130 includes at least a heat transferable dye, a binder resin, and a release agent, wherein the release agent is a polyether-modified silicone oil and a perfluoroalkyl compound; The weight ratio of the ether-modified silicone oil to the perfluoroalkyl compound is from 9: 1 to 6: 4.
As a result, the occurrence of peeling lines and abnormal transfer during thermal transfer can be prevented without blurring or background contamination of the image.

(2) In the thermal transfer recording medium 1 according to this embodiment, the content of the release agent is 0.5 to 3.0% by mass based on the binder resin contained in the dye layer 30.
Thereby, it is possible to prevent the occurrence of peeling lines and abnormal transfer during thermal transfer without blurring or background contamination of the image.

(3) In the thermal transfer recording medium 1 according to the present embodiment, the polyether-modified silicone oil has a molecular weight of 8000 or more.
As a result, bleeding of the image, background dirt, and the like are less likely to occur, and peeling lines and abnormal transfer during thermal transfer can be prevented.

(4) In the thermal transfer recording medium 1 according to the present embodiment, the coefficient of kinetic friction of each of the heat-resistant lubricating layer 40 with respect to SiC, Si ₃ N ₄ , and SiON at 80 ° C. or more and 160 ° C. or less is 0.18 or less. And
This suppresses wear of the thermal head of the printer when printing is repeatedly performed.

(5) In the heat-sensitive transfer recording medium 1 according to the present embodiment, the heat-resistant lubricating layer 40 includes at least a binder resin and a filler, and the filler has a particle diameter D50 of a thickness of the heat-resistant lubricating layer 40. And less than 20% by weight with respect to the heat-resistant lubricating layer 40.
This makes it difficult for the heat-resistant lubricating layer 40 to be stretched when a thermal pressure is applied thereto, thereby suppressing the thermal transfer recording medium 1 from being stretched at the time of thermal transfer and preventing print wrinkles from occurring.

(6) In the thermal transfer recording medium 1 according to the present embodiment, the elongation percentage in the MD direction when the thermal transfer recording medium 1 is heated while applying a load of 5000 N / m ² in the MD direction is 1%. Is 205 ° C. or higher.
Thereby, the elongation of the thermal transfer recording medium 1 during thermal transfer is suppressed, and the occurrence of print wrinkles can be prevented.

  Hereinafter, the materials used in each example and each comparative example of the present invention are shown. In the following description, “parts” is based on mass unless otherwise specified. Further, the present invention is not limited to the embodiments.

(Example 1)
<Preparation of base material with heat-resistant lubricating layer>
As a substrate, a 4.5 μm polyethylene terephthalate film was used, and a coating solution for a heat-resistant lubricating layer having the following composition was applied on one surface thereof by a gravure coating method to a coating amount of 1.0 g / m ² after drying. (Film thickness 0.60 μm) and dried at 100 ° C. for 1 minute. Thereafter, the substrate was aged in a 40 ° C. environment for one week to obtain a substrate having a heat-resistant lubricating layer.
<Coating liquid for heat-resistant lubricating layer-1>
・ Acrylic polyol resin 16.02 parts ・ Zinc stearate 1.50 parts ・ Talc (particle size (D50) 0.80 μm) 2.35 parts ・ 2,6-tolylene diisocyanate prepolymer 5.13 parts ・ Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

On the surface of the base material with the heat-resistant lubricating layer on which the heat-resistant lubricating layer is not applied, the coating amount for the undercoat layer after drying is 0.20 g / m ² by a gravure coating method. And then dried at 100 ° C. for 2 minutes to form an undercoat layer. Subsequently, a coating solution-1 for a dye layer having the following composition was applied onto the undercoat layer by a gravure coating method so that the coating amount after drying was 0.70 g / m ² , After drying for a minute, a dye layer was formed. Thus, the thermal transfer recording medium of Example 1 was obtained.
<Coating liquid for undercoat layer-1>
Polyvinyl alcohol 2.50 parts
Polyvinylpyrrolidone 2.50 parts
57.0 parts of pure water
38.0 parts of isopropyl alcohol <Dye layer coating liquid-1>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.054 parts, perfluoroalkyl compound 0.0006 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 2)
In the thermal transfer recording medium prepared in Example 1, the same procedure as in Example 1 was carried out except that the dye layer coating liquid applied to the substrate was changed to the dye layer coating liquid-2 having the following composition. A thermal transfer recording medium was obtained.
<Coating solution for dye layer-2>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.048 parts, perfluoroalkyl compound 0.012 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 3)
In the thermal transfer recording medium prepared in Example 1, the procedure of Example 3 was repeated in the same manner as in Example 1 except that the dye layer coating liquid applied to the substrate was changed to the dye layer coating liquid-3 having the following composition. A thermal transfer recording medium was obtained.
<Coating solution-3 for dye layer>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.042 parts, perfluoroalkyl compound 0.018 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 4)
In the thermal transfer recording medium prepared in Example 1, the procedure of Example 4 was repeated in the same manner as in Example 1 except that the dye layer coating liquid applied to the substrate was changed to the dye layer coating liquid-4 having the following composition. A thermal transfer recording medium was obtained.
<Dye layer coating solution-4>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts, perfluoroalkyl compound 0.024 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 5)
In the thermal transfer recording medium prepared in Example 1, the procedure of Example 5 was repeated in the same manner as in Example 1 except that the coating solution for the dye layer applied to the substrate was changed to a coating solution -5 for the dye layer having the following composition. A thermal transfer recording medium was obtained.
<Coating solution-5 for dye layer>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.096 parts, perfluoroalkyl compound 0.024 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 6)
In the heat-sensitive transfer recording medium prepared in Example 1, the procedure of Example 6 was repeated in the same manner as in Example 1 except that the coating solution for the dye layer applied to the substrate was changed to the coating solution -6 for the dye layer having the following composition. A thermal transfer recording medium was obtained.
<Coating solution-6 for dye layer>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.016 parts, perfluoroalkyl compound 0.004 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.98 parts

(Example 7)
In the heat-sensitive transfer recording medium prepared in Example 1, the same procedure as in Example 1 was carried out except that the dye layer coating liquid applied to the substrate was changed to the dye layer coating liquid -7 having the following composition. A thermal transfer recording medium was obtained.
<Coating solution for dye layer-7>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4957, Shin-Etsu Silicone Co., Ltd., molecular weight 5000) 0.048 parts, perfluoroalkyl compound 0.012 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Example 8)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 8 was obtained in the same manner as in Example 1 except that the temperature was changed to -2.
<Coating liquid for heat-resistant lubricating layer-2>
-17.63 parts of acrylic polyol resin-1.50 parts of zinc stearate-0.24 parts of talc (particle size (D50) 0.80 µm)-5.64 parts of 2,6-tolylene diisocyanate prepolymer-toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Example 9)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 9 was obtained in the same manner as in Example 1, except that the temperature was changed to -3.
<Coating solution-3 for heat-resistant lubricating layer>
• 16.91 parts of acrylic polyol resin • 1.50 parts of zinc stearate • 1.18 parts of talc (particle size (D50) 0.80 μm) • 5.31 parts of 2,6-tolylene diisocyanate prepolymer • toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Example 10)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 10 was obtained in the same manner as in Example 1 except that the temperature was changed to -4.
<Coating solution-4 for heat-resistant lubricating layer>
14.60 parts of an acrylic polyol resin; 1.50 parts of zinc stearate; 4.23 parts of talc (particle size (D50) 0.80 μm); 4.67 parts of 2,6-tolylene diisocyanate prepolymer; 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Example 11)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 11 was obtained in the same manner as in Example 1 except that the temperature was changed to -5.
<Coating solution for heat-resistant lubricating layer-5>
・ Acrylic polyol resin 16.36 parts ・ Zinc stearate 1.00 part ・ Talc (particle size (D50) 0.80 μm) 2.40 parts ・ 2,6-tolylene diisocyanate prepolymer 5.24 parts ・ Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Example 12)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 12 was obtained in the same manner as in Example 1 except that the temperature was changed to -6.
<Coating solution for heat-resistant lubricating layer-6>
15.68 parts of an acrylic polyol resin; 2.00 parts of zinc stearate; 2.30 parts of talc (particle size (D50) 0.80 μm); 5.02 parts of 2,6-tolylene diisocyanate prepolymer; 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Example 13)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Example 13 was obtained in the same manner as in Example 1 except that the temperature was changed to -7.
<Coating solution for heat-resistant lubricating layer-7>
-15.34 parts of acrylic polyol resin-2.50 parts of zinc stearate-2.25 parts of talc (particle size (D50) 0.80 µm)-4.91 parts of 2,6-tolylene diisocyanate prepolymer-toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Comparative Example 1)
In the heat-sensitive transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-8, the sensitivity of Comparative Example 1 was changed. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-8>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.120 parts, toluene 45.00 parts, methyl ethyl ketone 44.88 parts

(Comparative Example 2)
In the heat-sensitive transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-9, the sensitivity of Comparative Example 2 was changed in the same manner as in Example 1. A thermal transfer recording medium was obtained.
<Dye layer coating solution-9>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4957, Shin-Etsu Silicone Co., Ltd., molecular weight 5000) 0.120 parts, toluene 45.00 parts, methyl ethyl ketone 44.88 parts

(Comparative Example 3)
In the thermal transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid -10, the sensitivity of Comparative Example 3 was changed in the same manner as in Example 1. A thermal transfer recording medium was obtained.
<Dye layer coating solution-10>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether modified silicone oil (X-22-4957, Shin-Etsu Silicone Co., Ltd. molecular weight 5000) 0.280 parts, toluene 44.86 parts, methyl ethyl ketone 44.86 parts

(Comparative Example 4)
In the thermal transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-11, the sensitivity of Comparative Example 4 was changed in the same manner as in Example 1. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-11>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.030 parts, perfluoroalkyl compound 0.030 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Comparative Example 5)
In the heat-sensitive transfer recording medium prepared in Example 1, the same procedure as in Example 1 was carried out except that the coating solution for dye layer applied to the substrate was changed to the above-mentioned coating solution for dye layer-12. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-12>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.060 parts, perfluoroalkyl compound 0.060 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.88 parts

(Comparative Example 6)
In the heat-sensitive transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-13, the sensitivity of Comparative Example 6 was changed. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-13>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.018 parts, perfluoroalkyl compound 0.042 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.94 parts

(Comparative Example 7)
In the heat-sensitive transfer recording medium prepared in Example 1, the same procedure as in Example 1 was repeated except that the dye layer coating liquid applied to the substrate was changed to the aforementioned dye layer coating liquid-14. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-14>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, polyether-modified silicone oil (X-22-4272, Shin-Etsu Silicone Co., Ltd., molecular weight 10,000) 0.036 parts, perfluoroalkyl compound 0.084 parts (Megafax F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.88 parts

(Comparative Example 8)
In the thermal transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-15, the sensitivity of Comparative Example 8 was changed in the same manner as in Example 1. A thermal transfer recording medium was obtained.
<Dye layer coating solution-15>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, perfluoroalkyl compound 0.120 parts (MegaFac F-569 DIC Corporation)
・ Toluene 45.00 parts ・ Methyl ethyl ketone 44.88 parts

(Comparative Example 9)
In the heat-sensitive transfer recording medium prepared in Example 1, except that the dye layer coating liquid applied to the substrate was changed to the above-mentioned dye layer coating liquid-16, the sensitivity of Comparative Example 9 was changed. A thermal transfer recording medium was obtained.
<Dye layer coating liquid-16>
・ C. I. Solvent Blue 63 6.0 parts, polyvinyl acetal resin 4.0 parts, perfluoroalkyl compound 0.280 parts (MegaFac F-569 DIC Corporation)
・ Toluene 44.86 parts ・ Methyl ethyl ketone 44.86 parts

(Comparative Example 10)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Comparative Example 10 was obtained in the same manner as in Example 1 except that the temperature was changed to -8.
<Coating solution-8 for heat-resistant lubricating layer>
13.89 parts of acrylic polyol resin, 1.50 parts of zinc stearate, 5.17 parts of talc (particle diameter (D50) 0.80 μm) 4.44 parts of 2,6-tolylene diisocyanate prepolymer, toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Comparative Example 11)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. Except for setting to -9, a thermal transfer recording medium of Comparative Example 11 was obtained in the same manner as in Example 1.
<Coating solution for heat-resistant lubricating layer-9>
・ Acrylic polyol resin 12.46 parts ・ Zinc stearate 1.50 parts ・ Talc (particle size (D50) 0.80 μm) 7.05 parts ・ 2,6-tolylene diisocyanate prepolymer 3.99 parts ・ Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Comparative Example 12)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. Except for -10, a thermal transfer recording medium of Comparative Example 12 was obtained in the same manner as in Example 1.
<Coating solution for heat-resistant lubricating layer-10>
Acrylic polyol resin 16.02 parts Zinc stearate 1.50 parts Talc (particle size (D50) 0.40 μm) 2.35 parts 2,6-Tolylene diisocyanate prepolymer 5.13 parts Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Comparative Example 13)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Comparative Example 13 was obtained in the same manner as in Example 1, except that the temperature was changed to -11.
<Coating solution for heat-resistant lubricating layer-11>
・ 16.88 parts of acrylic polyol resin ・ 0.25 parts of zinc stearate ・ 2.48 parts of talc (particle size (D50) 0.80 μm) ・ 5.40 parts of 2,6-tolylene diisocyanate prepolymer ・ Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

(Comparative Example 14)
In the heat-sensitive transfer recording medium prepared in Example 1, the coating solution for the dye layer to be applied to the base material was the coating solution-5 for the dye layer described above, and the coating solution for the heat-resistant slip layer was the coating solution for the heat-resistant slip layer having the following composition. A thermal transfer recording medium of Comparative Example 14 was obtained in the same manner as in Example 1 except that the temperature was changed to -12.
<Coating solution for heat-resistant lubricating layer-12>
・ 16.70 parts of acrylic polyol resin ・ 0.50 parts of zinc stearate ・ 2.45 parts of talc (particle size (D50) 0.80 μm) ・ 5.35 parts of 2,6-tolylene diisocyanate prepolymer ・ Toluene 50. 00 parts ・ Methyl ethyl ketone 20.00 parts ・ Ethyl acetate 5.00 parts

<Preparation of transfer object>
A 188 μm white foamed polyethylene terephthalate film was used as a substrate, and a coating solution for an image receiving layer having the following composition was coated on one surface thereof by a gravure coating method so that the coating amount after drying was 5.0 g / m ^2. And dried. In this way, a transfer object for thermal transfer was produced.

<Coating solution for image receiving layer>
・ 19.5 parts of vinyl chloride-vinyl acetate-vinyl alcohol copolymer ・ 0.5 parts of amino-modified silicone oil ・ 40.0 parts of toluene ・ 40.0 parts of methyl ethyl ketone

<Evaluation of bleeding / dirt printing>
Printing was performed using a thermal transfer recording medium in Examples 1 to 13 and Comparative Examples 1 to 14 using a thermal simulator, and bleeding of the printed matter and background contamination were evaluated. The results are shown in Tables 1 and 2.
For the blur, a natural image (person image) was used, and for the background stain, a solid white image was used as an evaluation image.
The printing conditions are as follows.
・ Print environment: 23 ° C, 50% RH
・ Applied voltage: 29V
・ Line cycle: 0.9msec
・ Print density: 300 dpi for main scanning and 300 dpi for sub-scanning

The evaluation of bleeding / dirt was performed according to the following criteria. Δ or above is a level that does not cause any practical problems.
: Bleeding and background dirt are not observed. Δ: Bleeding and background dirt are slightly observed. △ ×: Bleeding and background dirt are partially recognized. ×: Bleeding and background dirt are observed. Recognized in

<Evaluation of peeling line and abnormal transfer>
In Examples 1 to 13 and Comparative Examples 1 to 14, using the thermal transfer recording medium cured at room temperature and the object to be transferred, the thermal transfer recording medium was subjected to black gradation with a thermal simulator at 48 ° C. and 5% environment. Printing was performed on 30 sheets, and the presence or absence of peeling marks or abnormal transfer was evaluated. The results are shown in Tables 1 and 2.
Evaluation of peeling line / abnormal transfer was performed based on the following criteria. Δ or above is a level that does not cause any practical problems. In the case where the transfer was abnormal, the peeling line could not be evaluated due to the transfer of the dye layer to the subject.
：: No peeling line / abnormal transfer was observed on the transferred body. △: Very little peeling line / abnormal transfer was found on the transferred body. △ ×: Peeling line / abnormal transfer was observed on the transferred body. , Partially observed ×: Peeling line / abnormal transfer to transferred object was observed on the entire surface

<Measurement of surface Si content (Si / C)>
In the present invention, the release agent component can be localized on the surface of the dye layer by mixing the polyether-modified silicone oil with the perfluoroalkyl compound. To confirm the effect, attention was paid to Si atoms contained in the polyether-modified silicone oil, and the amount of Si on the surface of the dye layer was measured. If the amount of Si is large, the amount of polyether-modified silicone oil present on the surface is large.

  The Si content is measured by X-ray electron spectroscopy. The measurement principle of X-ray photoelectron spectroscopy is to irradiate an element with X-rays and quantitatively and qualitatively detect the kinetic energy of specific free electrons emitted from atoms. Due to the characteristics of the measurement principle, this method measures elements constituting a surface of about 10 nm from the solid surface, and does not measure the entire thickness direction of the measurement object.

  The amount of Si on the surface of the dye layer was evaluated using an X-ray photoelectron spectrometer (trade name: ESCA1600, manufactured by ULVAC-PHI). The X-ray source used was MgKα, of which the accelerating voltage of the X-ray source was 15 kV. Among the elements having a binding energy in the measurement range of 10 to 1100 ev, C, Si, N, and O were qualitatively and quantitatively determined. By calculating C, the amount of the release agent on the surface of the dye layer was determined. The measurement range was about 0.8 mmφ. The results are shown in Tables 1 and 2.

  In the present invention, since both the polyether-modified silicone oil and the perfluoroalkyl compound have releasability from the object to be transferred, performance aspects such as peeling lines and abnormal transfer cannot be discussed only with the amount of surface Si.

<Evaluation of dynamic friction coefficient>
Tables 1 and 2 show the results of measuring the dynamic friction coefficients of the heat-resistant lubricating layers of the thermal transfer recording media of Examples 1 to 13 and Comparative Examples 1 to 14 with respect to SiC, Si ₃ N ₄ and SiON at 80 ° C., 120 ° C. and 160 ° C. Shown in The dynamic friction coefficient was measured at a load of 100 g and a scanning speed of 100 mm / min using HEIDON tribo gear 14 manufactured by Shinto Kagaku.

<Evaluation of thermal head wear>
The thermal transfer recording media of Examples 1 to 13 and Comparative Examples 1 to 14 were used, and three types of unused thermal heads of SiC, Si ₃ N ₄ and SiON were used. Printing was continuously performed on 10,000 sheets.
Printing environment: 23 ° C, 50% RH
Applied voltage: 29V
Line cycle: 0.9 msec
Printing density: main scanning 300 dpi sub-scanning 300 dpi

Then, the cross-sectional shape of the used thermal head was observed with a Nikon NEXIV VMR to confirm wear due to rubbing with the heat-resistant lubricating layer. Tables 1 and 2 show the evaluation results of the abrasion. The evaluation of wear was based on the following criteria.
〇: The maximum wear is less than 1 μm. The service life of the thermal head can be maintained at a practically acceptable level.
X: The maximum wear exceeds 1 μm. The life of the thermal head is shortened.

<Measurement of temperature at which elongation becomes 1%>
The measurement results of the temperature T of the thermal transfer recording media of Examples 1 to 13 and Comparative Examples 1 to 14 when the temperature at which the elongation rate when the sheet is heated while being stretched while applying a load is 1% are taken as the temperature T. The results are shown in Tables 1 and 2. Tables 1 and 2 show the measurement results of the temperature T of the sheets prepared in Examples 1 to 14 and Comparative Examples 1 to 14 without the heat-resistant lubricating layer.

The sample was cooled from room temperature to 0 ° C. at −5 ° C./min while pulling the sample with a load of 5000 N / m ^{2 in} the MD direction using TMA / SS6100 manufactured by SII, and then cooled to 260 ° C. by 5 ° C. It was derived by measuring the displacement of the sample when heated at / min.

<Print wrinkle evaluation>
Using the thermal transfer recording media of Examples 1 to 13 and Comparative Examples 1 to 14, using SiC, Si ₃ N ₄ , and SiON as the protective film of the thermal head, solid printing was performed with a thermal simulator to evaluate print wrinkles. did. As an evaluation of wrinkles, printing evaluation was performed at a speed of 10 inches / sec for two patterns in which printing energy was changed to 24 V and 27 V.

The evaluation of printing failure due to wrinkles was performed according to the following criteria. If wrinkles do not occur at a voltage of 24 V, there is no practical problem.
〇: No print failure due to wrinkles on prints ×: Print failure due to wrinkles in prints

From the results shown in Tables 1 and 2, Examples 1 to 7 in which the polyether-modified silicone oil and the perfluoroalkyl compound were mixed were compared with Comparative Examples 1 to 3, 8, and 9, which were used alone, respectively. -It was found that no bleeding, background contamination, and abnormal transfer occurred.
In Comparative Examples 4 and 5 in which the ratio of the polyether-modified silicone oil to the perfluoroalkyl compound was 5/5, and in Comparative Examples 6 and 7 in which the mixing ratio was 3/7, occurrence of peeling lines was confirmed. It was confirmed that the weight ratio of the ether-modified silicone oil to the perfluoroalkyl compound was effective in the range of 9: 1 to 6: 4.

  In Example 5 in which the release agent addition amount was 3%, bleeding and background soiling remained uneasy, and in Example 6 in which the addition amount was 0.5%, there was anxiety in the occurrence of peeling lines. It was confirmed that the content was preferably in the range of 5 to 3.0%.

  Also, from a comparison between Example 2 in which the molecular weight of the polyether-modified silicone oil is 8000 or more and Example 7 in which the molecular weight of the polyether-modified silicone oil is less than 8000, the one in which the molecular weight of the polyether-modified silicone oil is larger is more effective for bleeding and background soiling. That was confirmed.

  Further, although the relationship between the surface Si amount and the peeling line, bleeding, background stain, and abnormal transfer cannot be determined, from the comparison of the Si amount in Example 1 and Comparative Example 1, the dye layer was obtained by mixing the perfluoroalkyl compound. It was confirmed that the polyether-modified silicone oil was easily localized on the surface.

  From the results shown in Tables 1 and 2, the heat-sensitive transfer recording media of Examples 1 to 13 and Comparative Examples 1 to 12 in which the kinetic friction coefficient of the heat-resistant lubricating layer with respect to SiC at 80 ° C. or more and 160 ° C. or less was 0.18 or less were There is no problem in abrasion of the SiC thermal head due to rubbing with the heat-resistant lubricating layer. On the other hand, in Comparative Examples 13 and 14 in which the dynamic friction coefficient of SiC of the heat-resistant lubricating layer at 80 ° C. or more and 160 ° C. or less exceeds 0.18, the maximum abrasion caused by rubbing with the heat-resistant lubricating layer of the thermal head was 1 μm. It was confirmed that the service life was shortened.

In addition, from the results shown in Tables 1 and 2, the heat-resistant lubricating layers of Examples 1 to 13 and Comparative Examples 1 to 12 in which the dynamic friction coefficient of Si ₃ N ₄ at 80 ° C. or higher and 160 ° C. or lower was 0.18 or less The thermal transfer recording medium has no problem in abrasion caused by rubbing against the heat-resistant lubricating layer of the Si ₃ N ₄ thermal head. On the other hand, in Comparative Examples 13 and 14, in which the kinetic friction coefficient of Si ₃ N ₄ with the heat-resistant lubricating layer at 80 ° C. or more and 160 ° C. or less exceeded 0.18, the abrasion due to rubbing with the heat-resistant lubricating layer of the thermal head was the largest. It was confirmed that the wear exceeded 1 μm and the life was shortened.

  Further, from the results shown in Tables 1 and 2, the heat-sensitive transfer recordings of Examples 1 to 13 and Comparative Examples 1 to 12 in which the kinetic friction coefficient of the heat-resistant lubricating layer with respect to SiON at 80 ° C. to 160 ° C. was 0.18 or less were obtained. The medium has no problem in abrasion due to rubbing with the heat-resistant lubricating layer of the thermal head of SiON. On the other hand, in Comparative Examples 13 and 14 in which the dynamic friction coefficient of SiON with respect to SiON at 80 ° C. or more and 160 ° C. or less of the heat-resistant lubricating layer exceeded 0.18, the maximum abrasion caused by rubbing with the heat-resistant lubricating layer of the thermal head was 1 μm. It was confirmed that the service life was shortened.

As described above, the life of the thermal head of any of the thermal heads of SiC, Si ₃ N ₄ , and SiON is extended when the dynamic friction coefficient of the heat-resistant lubricating layer with respect to the head material at 80 ° C. to 160 ° C. It was confirmed that the level could be maintained without practical problems. It is considered that the friction between the thermal head, which becomes high in printing temperature, and the heat-resistant lubricating layer heated by the thermal head is reduced, so that the wear of the thermal head is suppressed.

From the results shown in Tables 1 and 2, the thermal transfer was performed when the temperature at which the elongation in the MD direction was 1% when the sheet was heated while applying a load of 5000 N / m ^{2 in} the MD direction was set to temperature T. In Examples 1 to 13 and Comparative Examples 1, 2, 4, 6, 7, 8, 13, and 14 in which the temperature T of the recording medium was 205 ° C. or higher, it was confirmed that no wrinkles occurred. On the other hand, in Comparative Examples 3, 5, and 9 to 12 in which the temperature T was lower than 205 ° C., print wrinkles occurred. From this, it was confirmed that print wrinkles did not occur when the temperature T was 205 ° C. or higher. This is presumably because if the temperature T is 205 ° C. or higher, the thermal transfer recording medium expands sufficiently when a heat pressure is applied.

  Further, from Examples 2, 5 and 6 in Tables 1 and 2, the larger the amount of the release agent added to the coating solution for the dye layer, the lower the temperature T of the heat-sensitive transfer recording medium having no heat-resistant lubricating layer. Accordingly, it was confirmed that the temperature T of the thermal transfer recording medium also decreased. From this, it is considered that as the release agent addition amount increases, the elongation rate of the thermal transfer recording medium when applying heat and pressure increases.

  Further, according to Examples 1 to 13 and Comparative Examples 1 to 9, 13 and 14 in Tables 1 and 2, the temperature of the heat-resistant lubricating layer was increased by including 20% by weight or less of talc as a filler. T was 205 ° C. or higher, and it was confirmed that print wrinkles did not occur. On the other hand, in Comparative Examples 10 and 11 in which talc (filler) was contained in an amount of 20% by weight or more, the temperature T of the heat-resistant lubricating layer was less than 205 ° C., and it was confirmed that print wrinkles occurred. . Thus, when the heat-resistant lubricating layer contains 20% by weight or less of the filler, the thermal transfer recording medium is prevented from elongation due to the heat pressure and print wrinkles do not occur. It has been found that when the agent is contained in the heat-resistant lubricating layer, the elongation due to the heat and pressure of the thermal transfer recording medium cannot be completely suppressed, and print wrinkles occur.

  From Examples 5 and Comparative Example 12 in Tables 1 and 2, when the particle diameter D50 of the filler contained in the heat-resistant lubricating layer is not less than the film thickness (0.60 μm) of the heat-resistant lubricating layer, the above-mentioned feeling is obtained. Although the effect of suppressing the elongation of the thermal transfer recording medium due to the heat pressure appears and no wrinkles occur on the print, if the particle diameter D50 of the filler is smaller than the thickness of the heat-resistant lubricating layer (0.60 μm), the heat of the thermal transfer recording medium is reduced. It has been confirmed that print wrinkles occur because elongation due to pressure cannot be suppressed.

  Although the present invention has been described with reference to a limited number of embodiments, the scope of rights is not limited thereto, and modifications of the embodiments based on the above disclosure will be obvious to those skilled in the art.

  The thermal transfer recording medium obtained by the present invention can be used in a sublimation transfer type printer, and can easily form various images in full color, in addition to increasing the speed and function of the printer. Therefore, it can be widely used for self-printing of digital cameras, cards such as identification cards, output products for amusement, and the like.

100: thermal transfer recording medium 110: base material 120: undercoat layer 130: dye layer 140: heat-resistant lubricating layer 141: binder resin etc. 142: filler 210: unwinding part 220: winding part 300: transfer object 400 : Thermal head 500: Platen roller

Claims (3)

A heat-sensitive transfer recording medium having a heat-resistant lubricating layer on one surface of a substrate and an undercoat layer and a dye layer on the other surface of the substrate in this order. Wherein the kinetic friction coefficient for each of SiC, Si ₃ N ₄ , and SiON in the following is 0.18 or less, and the dye layer contains at least a heat transferable dye, a binder resin, and a release agent; Comprises a polyether-modified silicone oil and a perfluoroalkyl compound, the ratio of the polyether-modified silicone oil to the perfluoroalkyl compound is 9: 1 to 6: 4 by weight, and the polyether-modified silicone oil has a molecular weight of 8,000. That is, the heat-resistant lubricating layer comprises at least a binder resin and a filler, and the filler has a particle diameter D50 equal to or greater than the thickness of the heat-resistant lubricating layer. A heat-sensitive transfer recording medium, wherein the content is less than 20% by weight based on the heat-resistant lubricating layer. When the heat-sensitive transfer recording medium is heated while being stretched in the MD direction of the substrate under a load of 5000 N / m ² per unit area of a cross section orthogonal to the MD direction of the substrate, the elongation percentage in the MD direction is as follows: 2. The thermal transfer recording medium according to claim 1, wherein the temperature at which 1% is reached is 205 ° C. or higher.   3. The thermal transfer recording medium according to claim 1, wherein the content of the release agent is 0.5 to 3.0% by mass based on the binder resin of the dye layer.

Images