JP6677918B2 - Transfer sheet - Google Patents

Description

  The present invention relates to a transfer sheet, and more particularly, to a transfer sheet including a base material and a hot-melt coloring layer containing a colorant and a (meth) acrylic resin on the base material.

  At present, a thermal transfer recording method is widely used as a simple printing method. The thermal transfer recording method can easily form various images, so that the number of printed sheets may be relatively small, such as the production of ID cards such as identification cards, business photographs, personal computer printers, video printers, and the like. Used in

  The thermal transfer sheet used in the thermal transfer recording system is roughly classified into a so-called melt transfer type, in which a hot melt coloring layer containing a coloring agent is melt-softened by heating and the hot melt coloring layer is transferred to an object to be transferred, that is, an image receiving sheet. It is classified into a thermal transfer sheet and a so-called sublimation type thermal transfer sheet in which the dye in the heat sublimation colored layer sublimates due to heat and the dye is transferred to the image receiving sheet. Here, when an ID such as an identification card is produced, particularly when a monotonous image such as a character or a number is formed, a heat transfer type heat transfer sheet is used.

  When a monotone image such as a character or a number is formed by using a heat-melting type thermal transfer sheet, there is a problem that the image is blurred or fogged. In order to solve this problem, Patent Document 1 proposes a transfer sheet including a base material and a colored layer containing an acrylic resin, a polyester resin, and a coloring agent.

  Such a problem that the image is blurred and fogged occurs particularly when an attempt is made to increase the printing speed for efficiency.

JP 2011-201180 A

  The present invention has been made in view of the background art described above, and has as its object to provide a printing method capable of printing without causing image blurring and blurring even when the printing speed is increased. The main object is to provide a transfer sheet with high stability.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the glass transition temperature of a release interface layer, which is not limited to a substrate and is transferred, (a hot-melt coloring layer or a release layer) is determined. It has been found that the above problem can be solved by including a polyester resin at 70 ° C. or higher. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A substrate, comprising a hot-melt coloring layer on the substrate,
A transfer sheet is provided, wherein the hot-melt coloring layer contains a polyester resin having a glass transition temperature of 70 ° C or higher.

That is, according to one aspect of the present invention,
Base material, on the base material, comprising a release layer and a hot-melt coloring layer in order,
A thermal transfer sheet is provided, wherein the release layer comprises a polyester resin having a glass transition temperature of 70 ° C or higher.

  In the above aspect of the present invention, it is preferable that the number average molecular weight of the polyester resin is 4,000 or more and 200,000 or less.

  In the above aspect of the present invention, the content of the polyester-based resin in the hot-melt coloring layer or the release layer is 2.5% by mass or more based on the total amount of solids in the hot-melt coloring layer or the release layer. It is preferably at most 0.0% by mass.

  In the above aspect of the present invention, it is preferable that the hot-melt coloring layer or the release layer contains a vinyl chloride-vinyl acetate resin.

  In the above aspect of the present invention, it is preferable that the hot-melt coloring layer contains a coloring agent and an acrylic resin having a glass transition temperature of 70 ° C or higher.

  In the above aspect of the present invention, it is preferable that a thermo-sublimation coloring layer is further provided so as to be face-sequential with the hot-melt coloring layer.

  Even when the printing speed is increased, high printing stability, that is, having high releasability from the base material and high adhesion to the transfer receiving body, and can prevent occurrence of blurring and blurring due to printing. Thus, it is possible to provide a transfer sheet capable of performing high-quality printing.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a transfer sheet according to the present invention. FIG. 1 is a schematic cross-sectional view showing one embodiment of a transfer sheet according to the present invention. FIG. 9 is a diagram illustrating a print pattern (white line and black line) of the transfer condition in the evaluation of the example.

  In the present specification, “parts”, “%”, “ratio”, and the like indicating the composition are based on mass unless otherwise specified. Further, in this specification, the “peeling interface layer” refers to a layer in contact with the peeling interface at the time of transfer.

<Transfer sheet>
In one embodiment, the transfer sheet according to the present invention comprises a substrate and a hot-melt colored layer. In this case, the substrate and the hot-melt coloring layer correspond to the peeling interface layer.
In one embodiment, the transfer sheet according to the present invention comprises a base material, a release layer and a hot-melt colored layer on the base material in this order. In this case, the release layer and the hot-melt coloring layer correspond to the release interface layer.
In one embodiment, the transfer sheet according to the present invention includes a substrate, and a release layer and a hot-melt colored layer on the substrate in this order. In this case, the substrate and the release layer correspond to the release interface layer.
In one embodiment, the transfer sheet according to the present invention includes a base material, and a release layer, a release layer, and a hot-melt colored layer on the base material in this order. In this case, the release layer and the release layer correspond to the release interface layer.
Further, in one embodiment, the transfer sheet according to the present invention may further include a back layer on the surface of the substrate opposite to the surface on which the hot-melt colored layer is formed. Hereinafter, the layer configuration of the transfer sheet according to the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic sectional view of an embodiment of the transfer sheet according to the present invention. The transfer sheet 10 shown in FIG. 1 includes a base material 11, a release layer 12, a release layer 13, and a hot-melt colored layer 14 on the base material 11 in this order. The back layer 15 is further provided on the surface opposite to the release layer 12.

  In one embodiment, the thermal transfer sheet 10 according to the present invention may include a substrate 11 and a hot-melt coloring layer 14 and a thermal sublimation coloring layer 16 on the substrate 11 in a plane-sequential manner (see FIG. 2).

  Hereinafter, each layer constituting the transfer sheet according to the present invention will be described in detail.

<Substrate>
In the present invention, the base material has a role of holding the hot-melt colored layer, and since heat is applied at the time of thermal transfer, it may be a material having a mechanical strength that does not hinder handling even in a heated state. preferable. Examples of the material for such a substrate include a polyethylene terephthalate (PET) film, a 1,4-polycyclohexylene dimethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a polystyrene film, a polypropylene film, a polysulfone film, and an aramid film. And cellulose derivatives such as polycarbonate film, polyvinyl alcohol film, cellophane and cellulose acetate, polyethylene film, polyvinyl chloride film, nylon film, polyimide film, and ionomer film. The thickness of the substrate is preferably 2 μm or more and 20 μm or less, more preferably 4 μm or more and 10 μm or less.

  As the substrate, a substrate whose surface has been subjected to an easy adhesion treatment may be used. Examples of the easy-adhesion treatment include a process of forming an easy-adhesion layer between a substrate and a hot-melt coloring layer described later. As such an easily adhesive layer, for example, a layer composed of aqueous acrylic, aqueous polyester, and aqueous epoxy compound is preferable. Aqueous acryl refers to a water-soluble or water-dispersible acrylic resin, and is preferably one containing alkyl acrylate or alkyl methacrylate as a main component. Is preferred. The aqueous polyester is a water-soluble or water-dispersible polyester-based resin, and examples of a component constituting the polyester-based resin include a polyvalent carboxylic acid and a polyvalent hydroxy compound. The aqueous epoxy compound is a compound containing a water-soluble or water-dispersible, preferably water-soluble epoxy group, and a compound containing at least one or more, preferably two or more epoxy groups in a molecule. is there. Examples of such an aqueous epoxy compound include glycidyl ethers of glycols, polyethers, polyols, glycidyl esters of carboxylic acids, and glycidyl-substituted amines, and are preferably glycidyl ethers. For the easy adhesion treatment, a method of forming an easy adhesion coating film on the surface of the base material is preferably used.

  In addition, as other easy adhesion treatments, treatments such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, and antistatic layer application on the surface of the base material are given. Can be

<Hot-melted colored layer>
In the present invention, the hot-melt colored layer is a printer having a thermal head for thermal transfer on the back side of the base material (the side on which the hot-melt colored layer is not provided) by superimposing a transfer sheet and an object to be transferred. This is a layer which is transferred onto the receiving layer provided on the transfer object or the intermediate transfer recording medium by heating using a conventionally known heating means. As described above, by transferring the hot-melt colored layer onto the transfer receiving body or the receiving layer provided on the intermediate transfer recording medium, it is possible to form images such as characters and numerals.

  When the hot-melt coloring layer corresponds to the peeling interface layer, it contains a polyester resin having a glass transition temperature (Tg) of 70 ° C. or more. The Tg of the polyester resin is more preferably 70 ° C. or more and 120 ° C. or less, and further preferably 80 ° C. or more and 100 ° C. or less. In addition, Tg can be obtained based on the measurement of the calorific value change (DSC method) by DSC (inspection scanning calorimetry).

  The number average molecular weight (Mn) of the polyester-based resin is preferably from 4,000 to 20,000, more preferably from 4,000 to 15,000, and still more preferably from 4,000 to 10,000. By setting the Mn of the polyester-based resin within the above numerical range, it is possible to prevent the occurrence of image blurring and blurring. Mn is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  When the hot-melt coloring layer corresponds to the peeling interface layer, the content of the polyester-based resin in the hot-melt coloring layer is 1.0% by mass or more based on the total amount of solids in the hot-melt coloring layer. It is preferably at most 2.5 mass%, more preferably at least 2.5 mass% and at most 50 mass%, even more preferably at least 5 mass% and at most 25 mass%. By setting the content of the polyester-based resin within the above numerical range, printing stability can be further ensured even when there is an influence of a printing environment, a temporal change, or the like.

  In the present specification, the polyester-based resin refers to a polymer having an ester group obtained by polycondensation of a polyhydric carboxylic acid and a polyhydric alcohol. Examples of the polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, dodecadicarboxylic acid, and cyclohexanedicarboxylic acid. . Examples of the polyhydric alcohol include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, decanediol, 2-ethyl-butyl-1-propanediol, and bisphenol. A and the like. Further, the polyester resin may be a copolymer of three or more kinds of polycarboxylic acids or polyhydric alcohols, or a copolymer with a monomer or polymer such as diethylene glycol, triethylene glycol, or polyethylene glycol. Is also good. Furthermore, in the present specification, the polyester-based resin also includes modified polyester-based resins. Examples of the modified polyester resin include a polyester urethane resin.

Further, it is preferable that the hot-melt coloring layer contains a vinyl chloride-vinyl acetate resin.
In the present invention, the vinyl chloride-vinyl acetate resin includes (1) a polymer of vinyl chloride and vinyl acetate or a derivative thereof, and (2) a copolymer of vinyl chloride and vinyl acetate with another monomer. It is a thing.
The total content of vinyl chloride and vinyl oxyacid in the vinyl chloride-vinyl acetate resin is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 100% by mass. .

  When the hot-melt coloring layer corresponds to the release interface layer, the content of the vinyl chloride-vinyl acetate-based resin in the hot-melt coloring layer is 20% by mass or more, It is preferably at most 0.5 mass%, more preferably at least 30 mass% and at most 80 mass%, even more preferably at least 40 mass% and at most 60 mass%. By setting the content of the vinyl chloride-vinyl acetate resin within the above numerical range, the printing density can be further increased, and the adhesion to the transfer receiving body can be improved. When the hot-melt coloring layer does not correspond to the release interface layer, the content of the vinyl chloride-vinyl acetate-based resin in the hot-melt coloring layer is 20% by mass or more, It is preferably at most 0.5 mass%, more preferably at least 30 mass% and at most 80 mass%, even more preferably at least 40 mass% and at most 60 mass%. By setting the content of the vinyl chloride-vinyl acetate resin within the above numerical range, the printing density can be further increased, and the adhesion to the transfer receiving body can be improved.

  Further, it is preferable that the hot-melt coloring layer contains a coloring agent and a (meth) acrylic resin. When the hot-melt coloring layer contains a (meth) acrylic resin, the transferability of the transfer sheet can be improved.

  As the coloring agent, conventionally known coloring agents can be used, but those having good characteristics as a printing material, for example, those having a sufficient coloring density and not discoloring by light, heat, temperature, etc. preferable. Further, it may be a substance that develops color by heating or a substance that develops color when it comes into contact with a component applied to the surface of the transfer-receiving body. The colorant preferably has at least one color selected from the group consisting of black, white, silver, cyan, magenta, yellow, red, green, and blue. For example, as a colorant, carbon black for black, titanium oxide for white, and inorganic material such as aluminum for silver, fluorescent light emitting material, infrared light emitting material, cyan, magenta, yellow, red, green, and blue C. I. It is preferable to use each pigment described in CI Pigment.

  The content of the colorant in the hot-melt coloring layer is preferably from 2.5% by mass to 80% by mass, and more preferably from 40% by mass to 60% by mass.

  Examples of the (meth) acrylic resin include poly (meth) acrylate, polymethyl (meth) acrylate, poly (meth) acrylamide, and styrene acrylic copolymer. Among these, polymethyl (meth) acrylate is particularly preferable because it can further improve heat resistance, scratch resistance, and transparency.

  The number average molecular weight (Mn) of the (meth) acrylic resin is preferably from 20,000 to 100,000, and more preferably from 20,000 to 100,000. By setting the Mn of the (meth) acrylic resin within the above numerical range, it is possible to prevent the occurrence of image blurring and blurring.

  The Tg of the (meth) acrylic resin is preferably from 70 ° C. to 110 ° C., more preferably from 90 ° C. to 110 ° C. By setting the Tg of the (meth) acrylic resin within the above numerical range, the heat resistance of the hot-melt colored layer can be improved, and the printing stability can be improved.

  When the hot-melt colored layer corresponds to the release interface layer, the content of the (meth) acrylic resin in the hot-melt colored layer is 20% by mass or more based on the total amount of solids in the hot-melt colored layer; The content is preferably 5% by mass or less, more preferably 30% by mass or more and 80% by mass or less, further preferably 40% by mass or more and 60% by mass or less. By setting the content of the (meth) acrylic resin within the above numerical range, it is possible to further increase the printing density and to improve the adhesion to the transfer target. When the hot-melt colored layer does not correspond to the peeling interface layer, the content of the (meth) acrylic resin in the hot-melt colored layer is 20% by mass or more based on the total amount of solids in the hot-melt colored layer; The content is preferably 5% by mass or less, more preferably 30% by mass or more and 80% by mass or less, even more preferably 40% by mass or more and 60% by mass or less. By setting the content of the (meth) acrylic resin within the above numerical range, it is possible to further increase the printing density and to improve the adhesion to the transfer target.

  The hot-melt colored layer is a polyvinyl alcohol resin, a polyvinyl acetate resin, a polyvinyl butyral resin, a polyvinyl acetal resin, a vinyl resin such as polyvinylpyrrolidone, a urethane resin such as polyurethane acrylate, an ethyl cellulose resin, Hydroxyethyl cellulose resin, ethyl hydroxy cellulose resin, methyl cellulose resin, cellulose resin such as cellulose acetate resin, polyamide resin, aromatic polyamide resin, polyamide resin such as polyamide imide resin, acetal resin, and polycarbonate resin May be.

The method for forming the hot-melt colored layer is not particularly limited, but it can be formed by a conventionally known coating method. For example, after adding the above-described materials in an appropriate solvent, and dissolving or dispersing the respective components to prepare a coating solution, the coating solution is coated on a substrate or the like by a gravure coating method, a roll coating method, It can be formed by applying and drying using known means such as a comma coat method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Further, the coating amount at the time of drying is preferably 0.2 g / m ² or more and 4.0 g / m ² or less, more preferably 0.5 g / m ² or more and 1.5 g / m ² or less. preferable.

<Release layer>
In the present invention, the release layer is a layer provided as required so that the hot-melt colored layer can be easily separated from the substrate during thermal transfer. When the transfer sheet includes a release layer, the release layer corresponds to the release interface layer, is provided between the base material and the hot-melt coloring layer, and is transferred to the transfer target together with the hot-melt coloring layer. .

  The release layer contains a polyester resin having a Tg of 70 ° C. or higher. The more preferable numerical range of Tg, the preferable numerical range of Mn, the content, and the like are the same as those described above.

  Further, the release layer preferably comprises a vinyl chloride-vinyl acetate resin. The preferred content of vinyl chloride-vinyl acetate resin is the same as described above.

  The release layer may contain a (meth) acrylic resin, a urethane resin, an acetal resin, a polyamide resin, a melamine resin, a polyol resin, a cellulose resin, or the like as long as the properties are not impaired.

  The release layer may further include an additive such as a release agent. As the release agent, a silicone oil and / or a wax component is used. By adding a release agent such as a silicone oil and a wax component to the release layer, it is possible to obtain a transfer sheet in which an image produced by printing is improved in blurring and blurring. Examples of the silicone oil include amino-modified silicone, epoxy-modified silicone, aralkyl-modified silicone, epoxy-aralkyl-modified silicone, alcohol-modified silicone, vinyl-modified silicone, and urethane-modified silicone, and it is preferable to use epoxy-modified silicone oil. Examples of the wax component include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, various low molecular weight polyethylenes, wood wax, beeswax, whale wax, Ibota wax, wool wax, shellac wax, candelilla wax, petrolactam, Various waxes such as partially modified wax, fatty acid ester, fatty acid amide and the like can be mentioned, and it is preferable to use polyethylene wax.

The method for forming the release layer is not particularly limited, but it can be formed by a conventionally known coating method. For example, after adding the polyester resin as described above and an additive such as a release agent as necessary in an appropriate solvent, and dissolving or dispersing each component, a coating solution is prepared. Forming by applying and drying on a material or a release layer using a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Can be. Further, the coating amount at the time of drying is preferably 0.2 g / m ² or more and 3.0 g / m ² or less, more preferably 0.5 g / m ² or more and 1.5 g / m ² or less. preferable.

<Release layer>
In the present invention, the release layer is a layer provided as desired so that the hot-melt colored layer or the peeling layer can be easily peeled off from the substrate during thermal transfer, and is a layer that stays on the substrate side during thermal transfer. is there. The release layer can be provided between the substrate and the hot-melt colored layer, or between the substrate and the release layer.

  The release layer is preferably formed of a material having a release property, and for example, preferably contains a binder resin and an additive such as a release agent. Examples of the binder resin include a (meth) acrylic resin, a urethane resin, an acetal resin, a polyamide resin, a melamine resin, a polyol resin, a cellulose resin, and a polyvinyl alcohol. It is preferable to use a resin. Examples of the release agent include a silicone oil, a phosphate ester plasticizer, a fluorine compound, a wax, a metal soap, a filler and the like, and it is preferable to use a silicone oil.

The method for forming the release layer is not particularly limited, but it can be formed by a conventionally known coating method. For example, the above-mentioned binder resin in an appropriate solvent and, if necessary, an additive such as a release agent, and the like, and a coating solution is prepared by dissolving or dispersing each component. It can be formed thereon by coating and drying using known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. The coating amount on drying, 0.02 g / ^{m 2} or more, preferably 1.0 g / ^{m 2} or less, 0.05 g / ^{m 2} or more, more not less 0.5 g / ^{m 2} or less preferable.

<Back layer>
In the present invention, the back layer is optionally used in order to prevent adverse effects such as sticking and wrinkles due to heating from the back side of the substrate (the side on which the hot-melt coloring layer is not provided) during thermal transfer. It is a layer provided. By providing the back layer, thermal printing is possible without sticking even in a thermal transfer sheet based on a plastic film having poor heat resistance, and the cutting of the plastic film, the ease of processing, etc. Take advantage of the benefits.

  The back layer preferably contains a binder resin and additives such as a slipping agent. Examples of the binder resin used for the back layer include an acrylic resin, a vinyl resin, a polyester resin, a urethane resin, a cellulose resin, a polyamide resin, an acetal resin, and a polycarbonate resin. Examples of the slip agent include metal soap, wax, silicone oil, fatty acid ester, filler, and talc.

The method for forming the back layer is not particularly limited, but can be formed by a conventionally known coating method. For example, the above binder resin and, if necessary, additives such as a slipping agent are added to an appropriate solvent, and each component is dissolved or dispersed to prepare a coating solution. It can be formed by applying and drying using known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method. Further, the coating amount at the time of drying is preferably 0.2 g / m ² or more and 3.0 g / m ² or less, more preferably 0.4 g / m ² or more and 1.5 g / m ² or less. preferable.

<Heat sublimation coloring layer>
The transfer sheet according to the present invention may have a heat sublimation coloring layer, if desired.
The heat sublimation colored layer preferably contains a sublimable dye, and preferably has a sufficient coloring density and does not discolor by light, heat, temperature or the like.
Sublimable dyes include, for example, diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine , Azomethine dyes such as pyridone azomethine, xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzeneazo dyes, pyridoneazo, thiophenazo Azo dyes, such as isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo and disazo, spiropyran dyes, indolinospiropyran dyes , Fluoran dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, quinophthalone-based dye can be used. More specifically, red dyes such as MSRedG (manufactured by Mitsui Toatsu Chemicals), Macrolex Red Violet R (manufactured by Bayer), CeresRed 7B (manufactured by Bayer), Samaron Red F3BS (manufactured by Mitsubishi Chemical), and holon brilliant Yellow dyes such as Yellow 6GL (manufactured by Clariant), PTY-52 (manufactured by Mitsubishi Kasei), Macrolex Yellow 6G (manufactured by Bayer), Kayaset Blue 714 (manufactured by Nippon Kayaku), Waxolin Blue AP-FW (Manufactured by ICI), Holon Brilliant Blue SR (manufactured by Sando), MS Blue 100 (manufactured by Mitsui Toatsu Chemicals), C.I. I. Blue dyes such as Solvent Blue 22 can be used.

  The heat sublimation coloring layer preferably contains a binder resin such as a cellulose resin, a vinyl resin, a (meth) acrylic resin, a polyurethane resin, a polyamide resin, and a polyester resin. Among the binder resins described above, cellulose resins, vinyl resins, (meth) acrylic resins, urethane resins and polyester resins are preferred from the viewpoint of excellent heat resistance and dye transferability, and vinyl resins are preferred. More preferred are polyvinyl butyral and polyvinyl acetoacetal.

As a method for forming the thermal sublimation coloring layer, for example, the following method can be mentioned. To the dye and the binder resin, if necessary, an additive such as a release agent is added, and dissolved in a suitable organic solvent such as toluene or methyl ethyl ketone, or a coating liquid for a heat sublimation colored layer obtained by dispersing in water. (Dissolution or dispersion) is applied to one surface of a substrate by a gravure printing method, a reverse roll coating method using a gravure plate, a roll coater, a bar coater, or the like, and dried. Can be formed. Further, the coating amount at the time of drying is preferably 0.2 g / m ² or more and 1.5 g / m ² or less, more preferably 0.4 g / m ² or more and 1.0 g / m ² or less. preferable.

<Transfer object>
The transfer object that can be used for the transfer of the transfer sheet according to the present invention is not particularly limited, and may be any of plain paper, woodfree paper, tracing paper, plastic film, glass, metal, ceramics, wood, cloth, and the like. You may.

<Transfer method>
The transfer of the hot-melt colored layer to the transfer object can be performed directly on the transfer object by using a conventionally known thermal transfer printer, and when the transfer object is difficult to directly transfer. Alternatively, the transfer may be performed by transferring the hot-melt coloring layer onto the receiving layer provided on the intermediate transfer recording medium, and then transferring the receiving layer of the intermediate transfer recording medium to the transfer target.
For the thermal transfer printer, for example, the transfer conditions may be set separately such as for sublimation transfer, for hot-melt transfer, and for protective layer transfer, or may be performed by appropriately adjusting the printing energy for each with a common printer. You may. The heating means is not particularly limited, and the transfer may be performed using a hot plate, a hot stamper, a hot roll, a line heater, an iron, or the like.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
As a substrate, a release layer coating solution having the following composition was applied on a 4.5 μm-thick PET film so as to have a dry composition of 1.0 g / m ² to form a release layer. The content of the polyester resin in the release layer relative to the total amount of solids in the release layer was 5% by mass.
<Coating liquid for release layer>
-95 parts by mass of vinyl chloride-vinyl acetate resin (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL (hereinafter sometimes referred to as "CNL" in some cases))
・ 5 parts by mass of polyester resin (Tg: 82 ° C., Mn: 6000, manufactured by Unitika Ltd., trade name: UE-9885)
・ Methyl ethyl ketone / toluene (1/1) 200 parts by mass

Next, a coating liquid for a hot-melt colored layer having the following composition was applied on the release layer so as to be 1.0 g / m ² when dried to form a hot-melt colored layer.
<Coating solution for hot-melt colored layer>
100 parts by mass of carbon black dispersion (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
・ 40 parts by mass of vinyl chloride-vinyl acetate resin (Nissin Chemical Industry Co., Ltd., trade name: Solvain CL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

On the surface opposite to the surface of the substrate on which the release layer was formed, a coating solution for a back layer having the following composition was applied so as to be 1.0 g / m ² when dried to form a back layer, and a transfer sheet was obtained. Was.
<Coating liquid for back layer>
-Polyvinyl butyral resin 2.0 parts by mass (Sekisui Chemical Co., Ltd., trade name: Esrec BX-1)
-9.2 parts by mass of polyisocyanate (Dainippon Ink and Chemicals, Inc., trade name: Burnock D750)
-1.3 parts by mass of phosphate ester surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Plysurf A208N)
・ Talc 0.3 parts by mass (Nihon Talc Kogyo Co., Ltd., trade name: Micro Ace P-3)
・ Toluene 43.6 parts by mass ・ Methyl ethyl ketone 43.6 parts by mass

(Example 2)
Transfer sheet in the same manner as in Example 1 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 20% by mass. I got

(Example 3)
Transfer sheet in the same manner as in Example 1 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 40% by mass. I got

(Example 4)
Transfer sheet in the same manner as in Example 1, except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 100% by mass. I got

(Example 5)
A transfer sheet was obtained in the same manner as in Example 1, except that the composition of the coating liquid for a hot-melt colored layer was changed as described below without providing a release layer. The content of the polyester-based resin in the hot-melt colored layer relative to the total amount of solids in the hot-melt colored layer was 20.0% by mass.
<Coating solution for hot-melt colored layer>
100 parts by mass of carbon black dispersion (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
・ 22.8 parts by mass of vinyl chloride-vinyl acetate resin (trade name: Solvain CL, manufactured by Nissin Chemical Industry Co., Ltd.)
・ 17.2 parts by mass of polyester resin (Tg: 82 ° C., Mn: 6000, manufactured by Unitika Ltd., trade name: UE-9885)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Example 6)
The polyester resin was changed to Byron GK-640 (Tg: 79 ° C., Mn: 13000, manufactured by Toyobo Co., Ltd.), and the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was: A transfer sheet was obtained in the same manner as in Example 1, except that the addition amount of the polyester resin was changed so as to be 20% by mass.

(Example 7)
The polyester resin was changed to Byron 885 (Tg: 79 ° C., Mn: 8000, manufactured by Toyobo Co., Ltd.), and the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 20 mass %, And a transfer sheet was obtained in the same manner as in Example 1 except that the amount of the polyester-based resin added was changed so as to be%.

(Example 8)
The polyester resin was changed to Byron UR-1700 (Tg: 92 ° C., Mn: 16000, manufactured by Toyobo Co., Ltd.), and the content of the polyester resin in the release layer with respect to the total solid content in the release layer was A transfer sheet was obtained in the same manner as in Example 1, except that the addition amount of the polyester resin was changed so as to be 20% by mass.

(Example 9)
A transfer sheet was obtained in the same manner as in Example 1, except that the composition of the coating liquid for the hot-melt colored layer was changed as follows.
<Coating solution for hot-melt colored layer>
100 parts by mass of carbon black dispersion (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
Acrylic resin A 40 parts by mass (Tg: 105 ° C, Mw: 40000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-83)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Example 10)
Transfer sheet in the same manner as in Example 9 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 20% by mass. I got

(Example 11)
Transfer sheet in the same manner as in Example 9 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 40% by mass. I got

(Example 12)
The polyester resin was changed to Byron GK-640 (Tg: 79 ° C., Mn: 13000, manufactured by Toyobo Co., Ltd.), and the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was: A transfer sheet was obtained in the same manner as in Example 9, except that the addition amount of the polyester resin was changed so as to be 20% by mass.

(Example 13)
A 4.5 μm-thick PET film having one surface subjected to a surface easy-adhesion treatment using a water-dispersible acrylic resin was prepared. On one surface of this substrate, a coating liquid for a release layer having the following composition was applied so as to be 0.5 g / m ² when dried to form a release layer.
<Coating liquid for release layer>
・ 25 parts by weight of urethane resin ・ 75 parts by weight of acetal resin (Sekisui Chemical Co., Ltd., trade name: Eslek KS-5)
・ 1900 parts by mass of toluene / isopropyl alcohol (1/1)

  Next, a release layer, a hot-melt colored layer, and a back layer were formed in the same manner as in Example 2 except that the transfer layer was coated on the release layer, to obtain a transferable sheet.

(Comparative Example 1)
A transfer sheet was obtained in the same manner as in Example 1, except that the polyester resin was changed to Byron 200 (Tg: 65 ° C, Mn: 17000, manufactured by Toyobo Co., Ltd.).

(Comparative Example 2)
Transfer sheet in the same manner as in Example 1 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 20% by mass. I got

(Comparative Example 3)
Transfer sheet in the same manner as in Example 1 except that the amount of the polyester resin was changed so that the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 40% by mass. I got

(Comparative Example 4)
The polyester-based resin was changed to Byron 600 (Tg: 47 ° C., Mn: 16000, manufactured by Toyobo Co., Ltd.), and the content of the polyester-based resin in the release layer relative to the total amount of solids in the release layer was 20 mass %, And a transfer sheet was obtained in the same manner as in Example 1 except that the amount of the polyester-based resin added was changed so as to be%.

(Comparative Example 5)
The polyester resin was changed to Byron 220 (Tg: 53 ° C., Mn: 3000, manufactured by Toyobo Co., Ltd.), and the content of the polyester resin in the release layer with respect to the total amount of solids in the release layer was 20 mass%. %, And a transfer sheet was obtained in the same manner as in Example 1 except that the amount of the polyester-based resin added was changed so as to be%.

[Evaluation of transfer sheet performance]
Each of the transfer sheets manufactured in the above Examples and Comparative Examples was evaluated for printing stability.

Using the transfer sheets manufactured in the above Examples and Comparative Examples and the following test printer, the printing speed was 3 msec / line (printing voltage 17.8 V) and 1.5 msec / line (printing voltage 25.2 V). In each case, the print pattern was transferred onto the receiving layer of the intermediate transfer recording medium produced as described below. Whether the image is blurred or blurred (the better the reproducibility of the white thin line portion is, the less blurred the image is, and the better the reproducibility of the black thin line portion is the less blurred image) is visually checked. The evaluation was performed according to the evaluation criteria. The evaluation results are summarized in Table 1.
(Test printer)
Thermal head: KEE-57-12GAN2-STA (manufactured by Kyocera Corporation)
Heating element average resistance value: 3303 (Ω)
Print density in the main scanning direction: 300 dpi
Print density in the sub-scanning direction: 300 dpi
Printing start temperature: 35 (° C)
Pulse duty ratio: 85%
Print pattern: Print pattern shown in FIG. 3 (white line and black line)

<Preparation of intermediate transfer recording medium>
A coating solution for a release layer, a coating solution for a protective layer, and a coating solution for a receiving layer and a heat sealing layer having the following composition are sequentially coated on a 16 μm-thick PET film by a gravure reverse coating method, dried, and peeled. A transfer receiving body was obtained by forming a layer, a protective layer, and a heat-sealing layer serving as a receiving layer. Dry coating amount of the above each of the release layer 1.0 g / ^{m 2,} the protective layer is 2.0 g / ^{m 2,} the receiving layer and the heat seal layer was 1.5 g / ^{m 2.}
(Coating solution for release layer)
Acrylic resin 29 parts by mass (Tg: 105 ° C, Mw: 25000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-87)
・ 1 part by mass of polyester resin (Toyobo Co., Ltd., trade name: Byron 200)
・ Methyl ethyl ketone / toluene (1/1) 70 parts by mass (coating solution composition for protective layer)
・ 30 parts by mass of polyester resin (Toyobo Co., Ltd., trade name: Byron 200)
・ 70 parts by mass of methyl ethyl ketone / toluene (1/1) (Coating solution for receiving layer and heat sealing layer)
-20 parts by mass of vinyl chloride-vinyl acetate resin (Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL)
・ 1 part by mass of silicone oil ・ 79 parts by mass of methyl ethyl ketone / toluene (1/1)

<Evaluation criteria for blurring>
A: There is no blur and it is good.
B: Partially blurred, but legible.
C: There is blurring and it is difficult to read.
D: The whole is fuzzy and defective.
<Criterion evaluation standard>
A: There is no rub and it is good.
B: Partly fuzzy, but legible.
C: There are rubs and it is difficult to read.
D: The whole is frayed and defective.

DESCRIPTION OF SYMBOLS 10 Transfer sheet 11 Base material 12 Release layer 13 Release layer 14 Hot-melt coloring layer 15 Back layer 16 Thermal sublimation coloring layer

Claims (6)

A substrate, comprising a hot-melt coloring layer on the substrate,
The hot melt colored layer, the glass transition temperature observed contains a 70 ° C. or more polyester resins,
The hot-melt coloring layer is a peeling interface layer,
The hot-melt coloring layer contains a vinyl chloride-vinyl acetate resin,
With respect to the total amount of solids in the heat-molten colored layer, the vinyl chloride - vinyl acetate content of resin is state, and are more than 40 wt%,
A transfer sheet, further comprising a heat sublimation coloring layer so as to be surface-sequential with the hot melt coloring layer . Base material, on the base material, comprising a release layer and a hot-melt coloring layer in order,
The release layer contains a polyester resin having a glass transition temperature of 70 ° C. or higher,
The release layer is a release interface layer,
The release layer contains a vinyl chloride-vinyl acetate resin,
The transfer sheet, wherein the content of the vinyl chloride-vinyl acetate resin is 40% by mass or more based on the total amount of solids in the release layer. The transfer sheet according to claim 2 , further comprising a heat sublimation coloring layer so as to be face-sequential with the hot melt coloring layer. The transfer sheet according to any one of claims 1 to 3, wherein the polyester resin has a number average molecular weight of 4000 or more and 20000 or less. The content of the polyester-based resin in the hot-melt coloring layer or the release layer is 2.5% by mass or more and 50.0% by mass based on the total amount of solids in the hot-melt coloring layer or the release layer. The transfer sheet according to claim 1, wherein: The transfer sheet according to any one of claims 1 to 5, wherein the hot-melt coloring layer includes a coloring agent and a (meth) acrylic resin having a glass transition temperature of 70 ° C or higher.