JP2017056678A - Transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer sheet with high print stability that is free from image blur or collapse.SOLUTION: A transfer sheet comprises base material, and a thermofusion colored layer on the base material, the thermofusion colored layer comprises colorant and, as binder resin, (meth) acrylic resin and polyvinyl chloride-vinyl acetate resin, and the (meth) acrylic resin has a glass transition temperature of 80°C or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a transfer sheet, and more specifically, includes 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. To a transfer sheet.

  Currently, a thermal transfer recording method is widely used as a simple printing method. Since the thermal transfer recording method can easily form various images, printed materials that require a relatively small number of copies, such as creation of ID cards such as identification cards, business photographs, personal computer printers, video printers, etc. Is used.

  The transfer sheet used in the thermal transfer recording method is roughly classified into a so-called melt transfer type in which a heat-melt colored layer containing a colorant is melted and softened by heating, and the heat-melt colored layer is transferred to a transfer target, 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 sublimes due to heat and the dye moves to the image receiving sheet. Here, when an ID such as an identification card is produced, particularly when a monotonous image such as letters and numbers is formed, a heat melting type thermal transfer sheet is used.

  When a monotonous image such as letters and numbers is formed using a heat melting type thermal transfer sheet, there is a problem that blurring and blurring of the image occur. 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 colorant.

  However, the transfer sheet disclosed in Patent Document 1 has insufficient performance for preventing image blurring and blurring and has room for improvement.

JP 2011-201180 A

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a transfer sheet having high printing stability that does not cause blurring or blurring of an image.

  As a result of intensive studies to solve the above problems, the present inventors have found that a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin having a glass transition temperature of 80 ° C. or higher as a base material, a colorant, and a binder resin. It has been found that the above-mentioned problems can be solved by using a transfer sheet provided with a hot-melt colored layer comprising. 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 substrate and a hot-melt colored layer on the substrate,
The hot-melt colored layer comprises a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as a colorant and a binder resin,
A transfer sheet is provided in which the glass transition temperature of the (meth) acrylic resin is 80 ° C. or higher.

  In the said aspect of this invention, it is preferable that mass ratio of the (meth) acrylic-type resin contained in a hot-melt colored layer and a vinyl chloride-vinyl acetate type-resin is 19: 1 to 1: 1.

  In the said aspect of this invention, it is preferable that the weight average molecular weights of (meth) acrylic-type resin are 20000 or more and 100000 or less.

  In the said aspect of this invention, it is preferable to further provide a mold release layer between a base material and a hot-melt colored layer.

  In the said aspect of this invention, it is preferable to further provide the heat sublimation colored layer so that it may become surface-sequentially with a hot-melt colored layer.

  ADVANTAGE OF THE INVENTION According to this invention, the transfer sheet which has high printing stability which does not generate | occur | produce the blurring and blurring by a printing can be provided. Moreover, according to this invention, the transfer sheet which does not produce foil cutting etc. and has high transferability can be provided.

It is the schematic cross section which showed one Embodiment of the transfer sheet by this invention. It is the schematic cross section which showed one Embodiment of the transfer sheet by this invention. It is a figure which shows the printing pattern (white line and black line) of the transfer conditions in evaluation of an Example.

  In the present specification, “part”, “%”, “ratio” and the like indicating the composition are based on mass unless otherwise specified.

<Transfer sheet>
The transfer sheet according to the present invention includes a base material and a hot-melt colored layer, and may further include a release layer between the base material and the hot-melt colored layer to form a hot-melt colored layer of the base material. You may further provide a back surface layer in the surface on the opposite side to the made surface. Hereinafter, the layer structure of the transfer sheet according to the present invention will be described with reference to the drawings.

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

  In one embodiment, the thermal transfer sheet 10 according to the present invention may include a base material 11 and a hot-melt colored layer 13 and a thermal sublimation colored layer 14 on the base material 11 (see FIG. 2).

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

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

  As the base material, a surface 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 the base material and a hot-melt colored layer described later. As such an easy-adhesion layer, for example, those composed of aqueous acrylic, aqueous polyester and aqueous epoxy compound are preferable. The water-based acrylic is a water-soluble or water-dispersible acrylic resin, preferably having an alkyl acrylate or an alkyl methacrylate as a main component, and the component is 30 mol% or more and 90 mol% or less, and is common. A polymerized one is preferred. The water-based polyester is a water-soluble or water-dispersible polyester resin, and examples of components constituting the polyester resin include polyvalent carboxylic acids and polyvalent hydroxy compounds. An aqueous epoxy compound is a compound containing an epoxy group that is water-soluble or water-dispersible, preferably water-soluble, and contains at least one, preferably two or more epoxy groups in the molecule. is there. Examples of such aqueous epoxy compounds include glycols, polyethers, glycidyl ethers of polyols, glycidyl esters of carboxylic acids, glycidyl-substituted amines, and the like, but glycidyl ethers are preferred. For the easy adhesion treatment, a method of forming an easily adhesive coating film on the surface of the substrate is preferably used.

  Other easy adhesion treatments include corona discharge treatment, plasma treatment, ozone treatment, flame treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, and application of an antistatic layer to the surface of the substrate. It is done.

<Hot-melt colored layer>
In the present invention, the thermal melt colored layer is formed by superimposing a transfer sheet and a transfer medium or an intermediate transfer recording medium, and the back side of the substrate (the side on which the hot melt colored layer is not provided) is the thermal transfer thermal layer. It is a layer having a heat seal property, such as a printer having a head, which is transferred onto a receiving layer included in a transfer medium or an 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 medium or the receiving layer included in the intermediate transfer recording medium, images such as letters and numbers can be formed.

The hot-melt colored layer comprises a colorant and a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as 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, that is, the separation performance from the substrate is ensured, and the transferred object It is possible to further ensure coherence (heat sealability) to the ink and to prevent the occurrence of blurring and slippage due to printing.

  The mass ratio of the (meth) acrylic resin and the vinyl chloride-vinyl acetate resin contained in the hot-melt colored layer is preferably 19: 1 to 1: 1, and 9: 1 to 6: 4. It is more preferable that the ratio is 6: 1 to 7: 3. By making the content ratio of the (meth) acrylic resin and 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 solid content in the binder resin of the hot melt colored layer is preferably 20% by mass or more, and preferably 50% by mass or more. More preferably. 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 means (1) a polymer of acrylic acid or methacrylic acid monomer or derivative thereof, (2) a polymer of acrylic acid ester or methacrylic acid ester monomer or derivative thereof, (3) Copolymers or derivatives of acrylic acid or methacrylic acid monomers and other monomers, and (4) copolymers of acrylic acid or methacrylic acid ester monomers and other monomers or derivatives thereof.

Examples of the acrylic ester or methacrylic ester monomer include alkyl acrylate, alkyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, lauryl acrylate, and lauryl methacrylate.
Examples of other monomers include 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 these, polymethyl (meth) acrylate is particularly preferable because it ensures heat resistance, scratch resistance, and transparency.

  The glass transition temperature (Tg) of the (meth) acrylic resin is 80 ° C. or higher, and more preferably 95 ° C. or higher. By setting Tg of the (meth) acrylic resin in the above numerical range, the heat resistance of the hot-melt colored layer can be improved, and the printing stability can be improved. Moreover, it is preferable that Tg is 110 degrees C or less. Tg can be determined based on the measurement of the change in calorie (DSC method) by DSC (inspection scanning calorimetry).

  The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 20000 or more and 100000 or less, and more preferably 20000 or more and 80000 or less. By setting the Mw of the (meth) acrylic resin within the above numerical range, it is possible to prevent image blurring and blurring. In addition, Mw is the molecular weight by polystyrene conversion measured by gel permeation chromatography (GPC).

  In the present invention, the vinyl chloride-vinyl acetate resin includes (1) a polymer of vinyl hydrochloride and vinyl acetate or a derivative thereof, and (2) a copolymer of vinyl hydrochloride, vinyl acetate and other monomers. It is a waste.

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

  The degree of polymerization of the vinyl hydrochloride-vinyl acetate resin is preferably 100 or more and 800 or less, and 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 ensure the storage stability of the thermal transfer ribbon as well as the adhesion to the transfer target. In addition, the polymerization degree of vinyl chloride-vinyl acetate resin can be calculated from the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

  In addition, the hot-melt colored layer is used as a binder resin in the range not impairing its properties, such as polyvinyl alcohol resin, polyvinyl acetate resin, polyvinyl butyral resin, polyvinyl acetal resin, polyvinyl pyrrolidone and other vinyl resins, polyethylene terephthalate resin, polyethylene Polyester resins such as naphthalate trees, urethane resins such as polyurethane acrylate, cellulose resins such as ethyl cellulose resins, hydroxyethyl cellulose resins, ethyl hydroxy cellulose resins, methyl cellulose resins, and cellulose acetate resins, polyamide resins, aromatic polyamide resins, polyamides Polyamide resins such as imide resins, acetal resins, polycarbonate resins, and the like may be included.

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

  The colorant content in the hot-melt colored 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.

Although the formation method of a hot-melt colored layer is not specifically limited, It can form by a conventionally well-known coating method. For example, after adding a coloring agent and a (meth) acrylic resin as described above in an appropriate solvent and dissolving or dispersing each component to prepare a coating solution, the coating solution is applied onto a substrate or the like. 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. 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 desired 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 base material and the hot-melt colored layer.

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

The method for forming the release layer is not particularly limited, but can be formed by a conventionally known coating method. For example, after adding the binder resin and an additive such as a mold release agent in an appropriate solvent and dissolving or dispersing each component to prepare a coating solution, the coating solution is applied to the base material. Furthermore, it can be formed by applying and drying 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. 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 formed in order to prevent adverse effects such as sticking and wrinkles due to heating from the back side of the base material (the side where the base material is not provided with the hot-melt colored layer) during thermal transfer. It is a layer to be provided. By providing a back layer, thermal printing can be performed without causing sticking even in a thermal transfer sheet based on a plastic film with poor heat resistance, and the plastic film is difficult to cut, easy to process, etc. Benefit from the benefits.

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

Although the formation method of a back layer is not specifically limited, It can form by a conventionally well-known coating method. For example, after adding the above-mentioned binder resin and an additive such as a slipping agent in an appropriate solvent and dissolving or dispersing each component to prepare a coating solution, the coating solution is applied to the substrate. Furthermore, it can be formed by applying and drying 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. Also, 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 include a heat sublimation colored layer as desired.
The heat sublimation colored layer preferably contains a sublimable dye, and preferably has a sufficient color density and does not discolor due to light, heat, temperature, or the like.
Sublimation dyes include, for example, diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazomethine, imidazolazomethine, 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, disazo, spiropyran dyes, indolino spiropyran 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 Chemical Co., Ltd.), Macrolex Red Violet R (manufactured by Bayer), CeresRed 7B (manufactured by Bayer), Samara 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 (Made by ICI), Holon Brilliant Blue SR (made by Sand), MS Blue 100 (made by Mitsui Toatsu Chemicals), C.I. I. Blue dyes such as Solvent Blue 22 can be used.

  The heat sublimation colored layer preferably comprises a binder resin such as a cellulose resin, a vinyl resin, a (meth) acrylic resin, a polyurethane resin, a polyamide resin, or a polyester resin. Among the above-mentioned binder resins, cellulose resins, vinyl resins, (meth) acrylic resins, urethane resins, and polyester resins are preferable from the viewpoint of excellent heat resistance, dye migration, and the like, and vinyl resins are preferred. More preferred are polyvinyl butyral and polyvinyl acetoacetal.

Examples of the method for forming the heat sublimation colored layer include the following methods. Coating solution for heat sublimation colored layer obtained by adding additives such as mold release agent to dye and binder resin as necessary and dissolving in appropriate organic solvent such as toluene and methyl ethyl ketone, or 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 material>
The transfer target that can be used for transfer of the transfer sheet according to the present invention is not particularly limited, and may be any of plain paper, fine paper, tracing paper, plastic film, glass, metal, ceramics, wood, cloth, and the like. May be.

<Transfer method>
The transfer of the hot-melt colored layer to the transfer target can be directly performed on the transfer target using a conventionally known thermal transfer printer.
In addition, when it is difficult to directly transfer the transfer object, after transferring the hot-melt colored layer onto the receiving layer of the intermediate transfer recording medium (primary transfer), the receiving layer of the intermediate transfer recording medium It can also be carried out by transferring (retransferring) to the transfer medium.
For thermal transfer printers, for example, transfer conditions may be set separately such as for sublimation transfer, thermal melt transfer, and protective layer transfer. May be. The heating means is not particularly limited, and transfer may be performed using a hot plate, a hot stamper, a hot roll, a line heater, an iron, or the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1
A PET film having a thickness of 4.5 μm was prepared as a substrate.

A release layer was formed by applying a release layer coating solution having the following composition to one surface of the substrate so as to be 0.2 g / m ² when dried.
<Release layer coating solution>
-Urethane resin 25 parts by mass-Acetal resin 75 parts by mass (manufactured by Sekisui Chemical Co., Ltd., trade name: ESREC KKS-5)
・ Toluene / isopropyl alcohol (1/1) 1900 parts by mass

Next, a hot melt colored layer was formed by applying a coating solution for hot melt colored layer having the following composition on the release layer so as to be 1.0 g / m ² upon drying. The ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
-(Meth) acrylic resin A 40 parts by mass (Tg: 105 ° C., Mw: 40000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialal BR-83)
Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C., degree of polymerization: 200, manufactured by Nissin Chemical Industry 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 base material on which the hot-melt colored layer is formed, a back layer coating solution having the following composition is applied so as to be 0.8 g / m ² when dried, and a back layer is formed. 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 Chemical Co., Ltd., trade name: Barnock D750)
-1.3 parts by mass of phosphate ester surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf A208N)
・ 0.3 parts by mass of talc (Nippon Talc Industry Co., Ltd., trade name: Microace P-3)
・ Toluene 43.6 parts by mass ・ Methyl ethyl ketone 43.6 parts by mass

(Example 2)
The composition of the coating solution for the hot melt colored layer is such that the ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer is 9: A transfer sheet was obtained in the same manner as in Example 1 except that it was changed to 1.

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

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

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

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

(Example 7)
Other than changing the acrylic resin A contained in the coating solution for the hot melt colored layer to an acrylic resin C (Tg: 90 ° C., Mw: 85000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialal BR-75) In the same manner as in Example 1, a transfer sheet was obtained.

(Example 8)
Other than changing the acrylic resin A contained in the coating solution for the hot melt colored layer to an acrylic resin D (Tg: 80 ° C., Mw: 65000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialal BR-77) 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 solution for the hot melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating liquid for hot melt colored layer>
-Titanium oxide dispersion 100 parts by mass (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: Solvein 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 solution for the hot melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating liquid for hot melt colored layer>
-Yellow pigment dispersion 100 parts by mass (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: Solvein 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 solution for the hot melt colored layer was changed to one having the following composition.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
・ 40 parts by mass of vinyl chloride-vinyl acetate resin (Tg: 70 ° C., polymerization degree: 300, manufactured by Nissin Chemical Industry 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 solution for the hot melt colored layer was changed to one having the following composition.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
・ 40 parts by mass of vinyl chloride-vinyl acetate resin (Tg: 76 ° C., polymerization degree: 200, manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvein 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 solution for the hot melt colored layer was changed to one having the following composition.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
-(Meth) acrylic resin A 40 parts by mass (Tg: 105 ° C., Mw: 40000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialal 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 solution for the hot melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (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: Dialal BR-64)
Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C., degree of polymerization: 200, manufactured by Nissin Chemical Industry 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 solution for the hot melt colored layer was changed to one having the following composition. The ratio of the content of the (meth) acrylic resin and the content of the vinyl chloride-vinyl acetate resin in the hot melt colored layer was 4: 1 on a mass basis.
<Coating liquid for hot melt colored layer>
Carbon black dispersion 100 parts by mass (solid content 46%, carbon black 40%, dispersant 6%, methyl ethyl ketone / toluene = 50/50)
-(Meth) acrylic resin F 40 parts by mass (Tg: 50 ° C., Mw: 45000, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialal BR-116)
Vinyl chloride-vinyl acetate resin 10 parts by mass (Tg: 76 ° C., degree of polymerization: 200, manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvain CNL)
・ Methyl ethyl ketone / toluene (1/1) 50 parts by mass

[Performance evaluation of transfer sheet]
The transfer stability of the transfer sheets produced in the above examples and comparative examples was evaluated.

Print stability (primary transfer)
Using the transfer sheets produced in the above Examples and Comparative Examples and the following test printer, the line cycle was 3 msec / line, and the printing voltages were 16.5 V, 18.0 V, and 19.5 V, respectively. The printing pattern (printing pattern shown in FIG. 3) was transferred onto the receiving layer of the intermediate transfer recording medium produced as described below. Visually confirm that there is blurring and blurring in the image (the better the reproducibility of the white thin line portion, the less the blurring of the image, and the better the reproducibility of the black thin line portion, the less the blurring of the image). 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: 3303 (Ω)
Main scanning direction printing density: 300 dpi
Sub-scanning direction printing density: 300 dpi
1 line cycle: 3.0 (msec.)
Printing start temperature: 35 (℃)
Pulse duty ratio: 85%

<Preparation of intermediate transfer recording medium>
On a PET film having a thickness of 16 μm, a peeling layer coating solution, a protective layer coating solution and a receiving layer / heat seal layer coating solution having the following composition are sequentially applied and dried by a gravure reverse coating method. A layer to be transferred was obtained by forming a layer, a protective layer and a receiving / heat sealing 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 weight 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)
-Polyester resin 30 parts by mass (trade name: Byron 200, manufactured by Toyobo Co., Ltd.)
・ Methyl ethyl ketone / toluene (1/1) 70 parts by mass (coating solution for receiving layer and heat seal layer)
・ 20 parts by mass of vinyl chloride-vinyl acetate resin (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Solvine CNL)
Silicone oil 1 part by mass (manufactured by 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: There is some blurring, but it can be read.
C: It is difficult to read because of blurring, but there is no problem in actual use.
D: There is blurring as a whole and it is defective.
<Evaluation standard for blur>
A: There is no slip and it is favorable.
B: Partially blurred, but readable.
C: It is difficult to interpret due to shakiness, but there is no problem in practical use.
D: Overall there is a slip and it is defective.

Retransferability (secondary transferability)
Intermediate transfer in which the printing pattern is transferred to the receiving layer from the intermediate transfer recording medium on which the printing pattern is transferred onto the receiving layer using the transfer sheets of the above examples and comparative examples. The transfer foil (peeling layer, protective layer and receiving layer / heat seal layer) of the medium was retransferred (secondary transfer). For this retransfer, a card laminator (manufactured by SIP) was used. The retransferability was evaluated visually according to the following evaluation items. The evaluation results are summarized in Table 1.
<Retransferability evaluation criteria>
A: Even if the transfer conditions were 160 ° C. and 2 sec / inch, the transfer foil could be transferred onto the transfer target without problems.
B: Under transfer conditions of 160 ° C. and 2 sec / inch, the adhesion between the transfer foil and the transfer object was low and transfer was not possible, but transfer was possible under the transfer conditions of 170 ° C. and 2 sec / inch without any problem.
C: Under transfer conditions of 170 ° C. and 2 sec / inch, the adhesion between the transfer foil and the transfer object was low and transfer was not possible, but at 180 ° C. and 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. and 2 sec / inch.

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

Claims (5)

A transfer sheet comprising a substrate and a hot-melt colored layer on the substrate,
The hot-melt colored layer comprises a (meth) acrylic resin and a vinyl chloride-vinyl acetate resin as a colorant and a binder resin,
The transfer sheet, wherein the glass transition temperature of the (meth) acrylic resin is 80 ° C. or higher.   The transfer sheet according to claim 1, wherein a mass ratio of the (meth) acrylic resin and the vinyl chloride-vinyl acetate resin contained in the hot-melt colored layer is 19: 1 to 1: 1.   The transfer sheet according to claim 1 or 2, wherein the (meth) acrylic resin has a weight average molecular weight of 20,000 or more and 100,000 or less.   The transfer sheet according to any one of claims 1 to 3, further comprising a release layer between the substrate and the hot-melt colored layer.   The transfer sheet according to any one of claims 1 to 4, further comprising a heat sublimation colored layer so as to be surface-sequential to the hot-melt colored layer.