JP6677919B2 - Transfer sheet - Google Patents

Description

  The present invention relates to a transfer sheet, and more particularly, to a transfer sheet, comprising a base material, and a hot-melt colored layer containing a colorant and a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin on the base material. The present invention relates to a transfer sheet comprising:

  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 transfer sheet used in the thermal transfer recording system is roughly classified into a so-called melt transfer type, in which the heat-melted coloring layer containing the colorant is melt-softened by heating and the hot-melt coloring layer is transferred to the transfer object, that is, the 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.

  However, the transfer sheet disclosed in Patent Literature 1 does not have sufficient performance to prevent blurring and blurring of an image, and there is room for improvement.

JP 2011-201180 A

  SUMMARY OF THE INVENTION The present invention has been made in view of the background art described above, and has as its main object to provide a transfer sheet having high printing stability without causing image blurring and blurring.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, as a base material, a colorant and a binder resin, a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin having a glass transition temperature of 80 ° C or higher. It has been found that the above problem can be solved by using a transfer sheet provided with a hot-melt coloring layer containing The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A transfer sheet comprising a base material and a hot-melt coloring layer on the base material,
The hot-melt coloring layer contains a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as a coloring agent and a binder resin,
A transfer sheet characterized in that the (meth) acrylic resin has a glass transition temperature of 80 ° C. or higher.

  In the above aspect of the present invention, the mass ratio of the (meth) acrylic resin and the vinyl chloride-vinyl acetate resin contained in the hot-melt coloring layer is preferably from 19: 1 to 1: 1.

  In the above aspect of the present invention, the weight average molecular weight of the (meth) acrylic resin is preferably from 20,000 to 100,000.

  In the above aspect of the present invention, it is preferable that a release layer is further provided between the substrate and the hot-melt colored layer.

  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.

  According to the present invention, it is possible to provide a transfer sheet having high printing stability without causing blurring and blurring due to printing. Further, according to the present invention, it is possible to provide a transfer sheet having high transferability without occurrence of foil breakage.

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.

<Transfer sheet>
The transfer sheet according to the present invention comprises a base material and a hot-melt coloring layer, and may further include a release layer between the base material and the hot-melt coloring layer, forming a hot-melt coloring layer of the base material. A back layer may be further provided on a surface opposite to the surface on which the light is applied. 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 and a hot-melt coloring layer 13 on the base material 11 in this order. On the opposite surface, a back layer 14 is further provided.

  In one embodiment, the thermal transfer sheet 10 according to the present invention may include a substrate 11 and a hot-melt coloring layer 13 and a thermal sublimation coloring layer 14 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. Polymerized ones are 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 coloring layer is formed by laminating a transfer sheet and a transfer medium or an intermediate transfer recording medium, and forming a back side of the base (a side on which the hot-melt coloring layer of the base is not provided) by a thermal transfer thermal transfer layer. This is a layer having a heat seal property, 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 such as a printer having a head. 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.

The hot-melt coloring layer contains a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as a coloring agent and a binder resin.
Since the hot-melt colored layer contains a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin, the printing stability of the transfer sheet is improved. This makes it possible to further ensure compatibility with the adhesiveness (heat-sealing property) to the ink, and to prevent the occurrence of blurring and rubbing due to printing.

  The mass ratio between the (meth) acrylic resin and the vinyl chloride-vinyl acetate resin contained in the hot-melt coloring layer is preferably from 19: 1 to 1: 1 and from 9: 1 to 6: 4. More preferably, it is still more preferably 6: 1 to 7: 3. By setting the content ratio of the (meth) acrylic resin to the vinyl chloride-vinyl acetate resin within the above numerical range, the printing stability of the transfer sheet can be more remarkably improved.

  The total content of the (meth) acrylic resin and the vinyl chloride-vinyl acetate resin relative to the total amount of solids in the binder resin of the hot-melt colored layer is preferably 20% by mass or more, and more preferably 50% by mass or more. More preferably, there is. Moreover, it is preferable that it is 100 mass% or less. By setting the total content within the above numerical range, the printing stability of the transfer sheet can be further improved.

  In the present invention, “(meth) acryl” includes both “acryl” and “methacryl”. The (meth) acrylic resin includes (1) a polymer of an acrylic acid or methacrylic acid monomer or a derivative thereof, (2) a polymer of an acrylic acid ester or a methacrylic ester monomer or a derivative thereof, (3) It includes a copolymer of acrylic acid or methacrylic acid monomer with another monomer or a derivative thereof, and (4) a copolymer of acrylic acid or methacrylic ester monomer with another monomer or a derivative thereof.

Examples of the acrylate or methacrylate monomer include alkyl acrylate, alkyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, lauryl acrylate, and lauryl methacrylate.
Other monomers include, for example, aromatic hydrocarbons, aryl group-containing compounds, amide group-containing compounds and vinyl chloride, and more specifically, styrene, benzylstyrene, phenoxyethyl methacrylate, acrylamide, methacrylamide, and the like. .

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

  The glass transition temperature (Tg) of the (meth) acrylic resin is 80 ° C. or higher, and more preferably 95 ° C. or higher. 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. Further, Tg is preferably 110 ° C. or lower. In addition, Tg can be obtained based on the measurement of the calorific value change (DSC method) by DSC (inspection scanning calorimetry).

  The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably from 20,000 to 100,000, and more preferably from 20,000 to 80,000. By setting the Mw of the (meth) acrylic resin within the above numerical range, it is possible to prevent the occurrence of blurring and blurring of the image. Note that Mw is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  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 Tg of the vinyl chloride-vinyl acetate resin is preferably 50 ° C or higher and 100 ° C or lower, more preferably 60 ° C or higher and 80 ° C or lower. By setting the Tg of the vinyl chloride-vinyl acetate resin within the above numerical range, the adhesion to the transfer-receiving body can be improved.

  The polymerization degree of the vinyl chloride-vinyl acetate resin is preferably 100 or more and 800 or less, more preferably 150 or more and 400 or less. By setting the degree of polymerization of the vinyl chloride-vinyl acetate resin within the above numerical range, it is possible to secure the preservability of the thermal transfer ribbon as well as the adhesiveness to the transfer target. The degree of polymerization of the vinyl chloride-vinyl acetate resin can be calculated from the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  Further, the hot-melt coloring layer, as long as its properties are not impaired, as a binder resin, polyvinyl alcohol resin, polyvinyl acetate resin, polyvinyl butyral resin, polyvinyl acetal resin, vinyl resins such as polyvinyl pyrrolidone, polyethylene terephthalate resin, polyethylene Polyester resin such as naphthalate tree, urethane resin such as polyurethane acrylate, 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 A polyamide-based resin such as an imide resin, an acetal-based resin, and a polycarbonate-based resin may be included.

  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 coloring agent in the hot-melt coloring layer is preferably 20% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 80% by mass or less.

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, a colorant and a (meth) acrylic resin as described above 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 0.5 g / m ² or more and 10 g / m ² or less, and more preferably 0.8 g / m ² or more and 5 g / m ² or less.

<Release layer>
In the present invention, the release layer is a layer provided as needed so that the hot-melt colored 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. The release layer can be provided between the substrate and the hot-melt colored 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. Further, the coating amount at the time of drying is preferably 0.1 g / m ² or more and 1.0 g / m ² or less, more preferably 0.2 g / m ² or more and 0.6 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 2.0 g / m ² or less, more preferably 0.4 g / m ² or more and 1.2 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 1.2 g / m ² or less, more preferably 0.3 g / m ² or more and 0.6 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.
When it is difficult to perform direct transfer on the transfer object, after transferring the heat-melt coloring layer onto the receiving layer of the intermediate transfer recording medium (primary transfer), the receiving layer of the intermediate transfer recording medium is used. Can be also transferred to the transfer target (re-transfer).
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 PET film having a thickness of 4.5 μm was prepared.

On one surface of this substrate, a release layer coating solution having the following composition was applied so as to be 0.2 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: Esrec K KS-5)
・ 1900 parts by mass of toluene / isopropyl alcohol (1/1)

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. The ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<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 (meth) acrylic resin A (Tg: 105 ° C, Mw: 40000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-83)
-Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C, polymerization degree: 200, manufactured by Nissin Chemical Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

On the surface opposite to the surface of the substrate on which the hot-melt colored layer is formed, a coating solution for a back layer having the following composition is applied so as to be 0.8 g / m ² when dried to form a back layer. I got
<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)
The composition of the coating liquid for a hot-melt colored layer was prepared such that the ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate-based resin in the hot-melt colored layer was 9: A transfer sheet was obtained in the same manner as in Example 1, except that the transfer sheet was changed to 1.

(Example 3)
The composition of the coating liquid for a hot-melt colored layer was prepared such that the ratio of the content of the (meth) acrylic resin in the hot-melt colored layer to the content of the vinyl chloride-vinyl acetate resin was 1: 1: A transfer sheet was obtained in the same manner as in Example 1, except that the transfer sheet was changed to 1.

(Example 4)
The composition of the coating liquid for a hot-melt colored layer was prepared such that the ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate-based resin in the hot-melt colored layer was 19: A transfer sheet was obtained in the same manner as in Example 1, except that the transfer sheet was changed to 1.

(Example 5)
The composition of the coating liquid for a hot-melt colored layer was prepared such that the ratio of the content of the (meth) acrylic resin in the hot-melt colored layer to the content of the vinyl chloride-vinyl acetate resin was 1: 1: A transfer sheet was obtained in the same manner as in Example 1, except that the transfer sheet was changed to 4.

(Example 6)
Except that the acrylic resin A contained in the hot-melt colored layer coating liquid was changed to an acrylic resin B (Tg: 105 ° C, Mw: 85000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-52). In the same manner as in Example 1, a transfer sheet was obtained.

(Example 7)
Acrylic resin A (Tg: 90 ° C., Mw: 85000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-75) was used instead of acrylic resin A contained in the hot-melt colored layer coating liquid. In the same manner as in Example 1, a transfer sheet was obtained.

(Example 8)
Acrylic resin A (Tg: 80 ° C., Mw: 65000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-77) was used instead of acrylic resin A contained in the coating liquid for the hot melt colored layer. In the same manner as in Example 1, a transfer sheet was obtained.

(Example 9)
A transfer sheet was obtained in the same manner as in Example 1 except that the release layer was not provided.

(Example 10)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating solution for hot-melt colored layer>
100 parts by mass of titanium oxide dispersion (solid content 46%, titanium oxide 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
Acrylic resin D 40 parts by mass (Tg: 80 ° C, Mw: 65000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-77)
-Vinyl chloride-vinyl acetate resin 10 parts by mass (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Example 11)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating solution for hot-melt colored layer>
100 parts by mass of yellow pigment dispersion (solid content 46%, Disper Yellow 54 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
Acrylic resin D 40 parts by mass (Tg: 80 ° C, Mw: 65000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-77)
-Vinyl chloride-vinyl acetate resin 10 parts by mass (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Comparative Example 1)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition.
<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)
・ Vinyl hydrochloride-vinyl acetate resin 40 parts by mass (Tg: 70 ° C., polymerization degree: 300, manufactured by Nissin Chemical Co., Ltd., trade name: Solvain CL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Comparative Example 2)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition.
<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)
・ Vinyl hydrochloride-vinyl acetate resin 40 parts by mass (Tg: 76 ° C., polymerization degree: 200, manufactured by Nissin Chemical Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Comparative Example 3)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition.
<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 (meth) acrylic resin A (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

(Comparative Example 4)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<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 (meth) acrylic resin E (Tg: 55 ° C, Mw: 65000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-64)
-Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C, polymerization degree: 200, manufactured by Nissin Chemical Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

(Comparative Example 5)
A transfer sheet was obtained in the same manner as in Example 1, except that the coating liquid for the hot-melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin to the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<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 (meth) acrylic resin F (Tg: 50 ° C, Mw: 45000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dynal BR-116)
-Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C, polymerization degree: 200, manufactured by Nissin Chemical Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

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

Printing stability (primary transferability)
Using the transfer sheets manufactured in the above Examples and Comparative Examples, and the following test printer, one line cycle was 3 msec / line, and the printing voltages were 16.5 V, 18.0 V, and 19.5 V, respectively. The print pattern (print pattern shown in FIG. 3) 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
One line cycle: 3.0 (msec.)
Printing start temperature: 35 (° C)
Pulse duty ratio: 85%

<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 (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL)
・ 1 part by mass of silicone oil (Shin-Etsu Chemical Co., Ltd., trade name: X-22-3000T)
・ Methyl ethyl ketone / toluene (1/1) 79 parts by mass
A: There is no blur and it is good.
B: Partially blurred, but legible.
C: It is difficult to read due to blurring, but there is no problem in practical use.
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: Although it is difficult to read due to rubbing, there is no problem in actual use.
D: The whole is frayed and defective.

Retransferability (secondary transferability)
Intermediate transfer in which the print pattern is transferred to the receptor layer from an intermediate transfer recording medium in which the print pattern has been transferred onto the receptor layer using the transfer sheets of the above Examples and Comparative Examples, to a vinyl chloride card (transfer member). The transfer foil (release layer, protective layer, receiving layer and heat seal layer) of the medium was retransferred (secondary transfer). For this retransfer, a card laminator (manufactured by SIP) was used. The retransferability was visually evaluated according to the following evaluation items. The evaluation results are summarized in Table 1.
<Retransfer evaluation criteria>
A: Even when the transfer conditions were 160 ° C. and 2 sec / inch, the transfer foil could be transferred onto the transfer object without any problem.
B: Under the transfer condition of 160 ° C. 2 sec / inch, the transfer foil could not be transferred due to low adhesion between the transfer foil and the object to be transferred, but under the transfer condition of 170 ° C. 2 sec / inch, transfer was possible without any problem.
C: Under the transfer conditions of 170 ° C. 2 sec / inch, the transfer foil could not be transferred due to low adhesiveness between the transfer foil and the object to be transferred, but at 180 ° C. 2 sec / inch, transfer was possible without any problem.
D: The transfer foil could not be transferred onto the transfer target even at 180 ° C. for 2 sec / inch.

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

Claims (4)

Substrate, a transfer sheet comprising a hot-melt coloring layer on the substrate, a substrate, a combination of an intermediate transfer recording medium comprising a receiving layer on the substrate,
The hot-melt coloring layer contains a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as a coloring agent and a binder resin,
The (meth) acrylic resin has a glass transition temperature of 95 ° C. or higher,
Said (meth) acrylic resin contained in the hot melt colored layer, the vinyl chloride - mass ratio of the vinyl acetate resin, 19: 1 to 7: are three der,
The combination of a transfer sheet and an intermediate transfer recording medium, wherein the receiving layer is a layer to be transferred onto a transfer object .   The combination of the transfer sheet and the intermediate transfer recording medium according to claim 1, wherein the weight average molecular weight of the (meth) acrylic resin is 20,000 or more and 100,000 or less.   3. The combination of the transfer sheet and the intermediate transfer recording medium according to claim 1, further comprising a release layer between the base material and the hot-melt coloring layer.   The combination of the transfer sheet and the intermediate transfer recording medium according to any one of claims 1 to 3, further comprising a heat sublimation coloring layer so as to be face-sequential with the hot-melt coloring layer.