JP7200609B2 - heat transfer sheet - Google Patents

Description

The present invention relates to thermal transfer sheets.

A thermal transfer sheet provided with a transfer layer (referred to as a protective layer transfer sheet) is used for the purpose of protecting the surface of an object to be transferred, for example, an image formed on a thermal transfer image-receiving sheet or an image formed on a card substrate. In some cases, the transfer layer is transferred onto the transferred material using a transfer layer. Transfer-receiving objects (printed objects) to which the transfer layer has been transferred are used in a wide variety of applications, including ID cards such as identification cards, driver's licenses, and membership cards.

As a thermal transfer sheet having a transfer layer, for example, a thermal transfer sheet (protective layer transfer sheet) proposed in Patent Documents 1 and 2 is known. These thermal transfer sheets are said to be capable of imparting abrasion resistance and plasticizer resistance to images. In addition to this, various attempts have been made regarding thermal transfer sheets for the purpose of protecting images.

In addition, with the recent diversification of uses of printed matter, there is a demand for printed matter that can sufficiently suppress abrasion of images even in harsh environments.

Japanese Patent No. 3440103 Japanese Patent No. 4034856

SUMMARY OF THE INVENTION The main object of the present invention is to provide a thermal transfer sheet capable of producing a printed matter having good abrasion resistance.

A thermal transfer sheet according to an embodiment of the present disclosure for solving the above problems is a thermal transfer sheet including a base material and a transfer layer provided on the base material, wherein the transfer layer is formed on the base material. The transfer layer is provided so as to be peelable from the material side, and has a single layer structure or a laminated structure in which two or more layers are laminated, and at least one layer constituting the transfer layer includes a binder and two layers. Contains molybdenum sulfide.

Further, in the above thermal transfer sheet, the transfer layer has a laminated structure including a melted layer, and among the layers constituting the transfer layer, the layer located closer to the substrate than the melted layer is the It may contain a binder and molybdenum disulfide.

Further, in the above thermal transfer sheet, the transfer layer has a laminated structure including a receiving layer, and among the layers constituting the transfer layer, the layer positioned closer to the substrate than the receiving layer is the It may contain a binder and molybdenum disulfide.

In the above thermal transfer sheet, the transfer layer has a laminated structure in which three or more layers are laminated, and the layer containing the binder and molybdenum disulfide constitutes the transfer layer. It may be located between layers.

Further, in the above thermal transfer sheet, a coloring material layer may be provided on the base material in a frame-sequential manner with the transfer layer.

According to the thermal transfer sheet according to the embodiment of the present disclosure, it is possible to impart good abrasion resistance to printed matter produced by transferring the transfer layer.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the thermal transfer sheet of this indication. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the thermal transfer sheet of this indication. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the thermal transfer sheet of this indication. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the thermal transfer sheet of this indication. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the thermal transfer sheet of this indication. 1 is a schematic cross-sectional view showing an example of a printed matter produced using the thermal transfer sheet of the present disclosure; FIG. 1A to 1D are process charts showing an example of a method for producing a printed matter using the thermal transfer sheet of the present disclosure;

Hereinafter, the present invention will be described with reference to the drawings. It should be noted that the present invention can be implemented in many different modes and should not be construed as being limited to the description of the embodiments exemplified below. In addition, in order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example, and the interpretation of the present invention is not intended. It is not limited. Further, in the specification and each figure of the present application, the same reference numerals may be given to the same elements as those described above with respect to the already-appearing figures, and detailed description thereof may be omitted as appropriate.

<<Thermal transfer sheet>>
As shown in FIGS. 1 to 5, the thermal transfer sheet 100 according to the embodiment of the present disclosure (hereinafter referred to as the thermal transfer sheet of the present disclosure) includes a base material 1, and is provided on the base material 1. It has a transfer layer 10 that can be peeled off from the material 1 side. Hereinafter, each configuration of the thermal transfer sheet 100 of the present disclosure will be specifically described with an example.

(Base material)
The base material 1 is an essential component in the thermal transfer sheet 100 of the present disclosure, and holds the transfer layer 10 and the like. The material of the base material 1 is not limited, and preferably has heat resistance and mechanical properties. Examples of such a substrate 1 include polyester such as polyethylene terephthalate, polycarbonate, polyimide, polyetherimide, cellulose derivatives, polyethylene, polypropylene, polystyrene, acrylic resin, polyvinyl chloride, polyvinylidene chloride, nylon, polyether ether ketone, and the like. Various plastic films or sheets can be exemplified. The thickness of the base material 1 can be appropriately set according to the material of the base material 1 so that its strength and heat resistance are appropriate, and is generally 2.5 μm or more and 100 μm or less.

Further, when another arbitrary layer is provided between the substrate 1 and the transfer layer 10, for example, when a release layer is provided between the substrate 1 and the transfer layer 10, the substrate In order to improve the adhesion between the material 1 and any other layer, the surface of the substrate 1 on the side of the transfer layer 10 may be surface-treated. Examples of surface treatment methods include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, low-temperature plasma treatment, primer treatment, and grafting treatment.

(transfer layer)
As shown in FIGS. 1 to 5, a transfer layer 10 is provided on the substrate 1. FIG. The transfer layer 10 is a layer that is peeled off from the substrate 1 side and transferred onto the transferred body 50 . The illustrated transfer layer 10 is provided directly on the base material 1, but the transfer layer 10 is provided indirectly on the base material 1 via another layer (for example, a release layer). (not shown). As shown in FIG. 1, the transfer layer 10 may have a single layer structure, or as shown in FIGS. 2 to 5, may have a laminated structure in which two or more layers are laminated. .

Here, in the thermal transfer sheet 100 of the present disclosure, at least one layer constituting the transfer layer 10 contains molybdenum disulfide. Hereinafter, among the layers constituting the transfer layer 10, a layer containing molybdenum disulfide may be referred to as a molybdenum disulfide-containing layer.

According to the thermal transfer sheet 100 of the present disclosure, which has the transfer layer 10 including the molybdenum disulfide-containing layer 3, it is possible to impart good abrasion resistance to printed matter produced by transferring the transfer layer 10.

At present, the mechanism by which the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure can be transferred to impart good abrasion resistance to the printed matter produced is not clear. Prints produced by transferring layers have lower abrasion resistance than prints produced by transferring the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure.

When the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure exhibits a single layer structure, the transfer layer 10 becomes the molybdenum disulfide-containing layer 3 (see FIG. 1). On the other hand, when the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure has a laminated structure, at least one layer constituting the transfer layer may be the molybdenum disulfide-containing layer 3 (see FIGS. 2 to 5). . Also, two or more layers constituting the transfer layer 10 may both be the molybdenum disulfide-containing layer 3 (not shown).

Further, when the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure has a laminated structure in which three or more layers are laminated, the molybdenum disulfide-containing layer 3 may be positioned between the layers constituting the transfer layer 10. good. According to this embodiment, molybdenum disulfide can be prevented from falling off from the transfer layer 10, and good wear resistance can be maintained over a long period of time.

There is no limitation on the content of molybdenum disulfide with respect to the total mass of the molybdenum disulfide-containing layer 3, and compared with a transfer layer that does not contain molybdenum disulfide, the transfer layer 10 contains molybdenum disulfide. Abrasion resistance can be imparted. In other words, by transferring the transfer layer 10, abrasion resistance can be imparted to printed matter produced.

When the average particle size of molybdenum disulfide contained in the molybdenum disulfide-containing layer 3 is 1 μm or less, the content of molybdenum disulfide with respect to the total mass of the molybdenum disulfide-containing layer 3 is 3% by mass or more and 50% by mass. % by mass or less is preferable. Further, when the average particle size of molybdenum disulfide contained in the molybdenum disulfide-containing layer 3 is more than 1 μm and 3 μm or less, the content of molybdenum disulfide with respect to the total mass of the molybdenum disulfide-containing layer 3 is 3 mass. % or more and 50 mass % or less is preferable, and 8 mass % or more and 50 mass % or less is more preferable. Further, when the average particle size of molybdenum disulfide contained in the molybdenum disulfide-containing layer 3 exceeds 3 μm, the content of molybdenum disulfide with respect to the total mass of the molybdenum disulfide-containing layer 3 is 3% by mass or more50 % by mass or less is preferable, and 8% by mass or more and 30% by mass or less is more preferable. By setting the content of molybdenum disulfide to a preferable content, the transfer layer 10 can be provided with better abrasion resistance.

The upper limit of the content of molybdenum disulfide is also not limited, and can be appropriately determined in consideration of the binder contained in the molybdenum disulfide-containing layer 3, other components, and the like. As an example, the content of molybdenum disulfide is 50% by mass or less with respect to the total mass of the molybdenum disulfide-containing layer 3 . Molybdenum disulfide can be sufficiently retained in the molybdenum disulfide-containing layer 3 by setting the content of molybdenum disulfide to 50% by mass or less.

The particle size of molybdenum disulfide is not limited, and can be appropriately determined in consideration of the thickness of the molybdenum disulfide-containing layer 3 and the like. The average particle size of the molybdenum disulfide contained in the molybdenum disulfide-containing layer 3 may be larger or smaller than the thickness of the molybdenum disulfide-containing layer 3 . The average particle size of molybdenum disulfide is the average particle size calculated by the Fisher method (FSSS) or the average particle size calculated by the following calculation method, and is preferably 0.1 μm or more and 30 μm or less, and 0.1 μm or more and 20 μm. The following is more preferable, and 0.1 μm or more and 6 μm or less is even more preferable. In addition, the molybdenum disulfide-containing layer 3 has an average particle size calculated by the Fisher method (FSSS) or calculated by the following calculation method is 0.2 times or more the thickness of the molybdenum disulfide-containing layer 3. It is preferable to contain molybdenum disulfide twice or less.

(Method for calculating average particle size of molybdenum disulfide)
The average particle size of molybdenum disulfide can be determined by a method of directly measuring the size of primary particles from an electron micrograph of a vertical section of the thermal transfer sheet. Specifically, the minor axis diameter and major axis diameter of the primary particles are measured, and the average is taken as the particle diameter of the particles. and The same result can be obtained by using either transmission type (TEM) or scanning type (SEM) electron microscope.

The shape of molybdenum disulfide is not limited as long as it has various particle shapes.

The molybdenum disulfide-containing layer 3 contains molybdenum disulfide and a binder for holding the molybdenum disulfide. The binder can be determined according to the performance desired for the molybdenum disulfide-containing layer 3 . The binder may be a resin component or a non-resin component such as a wax component. The molybdenum disulfide-containing layer 3 has good wear resistance regardless of the type of binder contained in the molybdenum disulfide-containing layer 3 .

An example of the transfer layer 10 including the molybdenum disulfide-containing layer 3 described above will be described below. The transfer layer 10 exemplified below includes the molybdenum disulfide-containing layer 3 and can produce printed matter with good abrasion resistance. Also, the configuration of the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure is not limited to the forms exemplified below. Specifically, the transfer layer 10 only needs to satisfy the condition that the molybdenum disulfide-containing layer 3 is included.

(Transfer layer of the first form)
FIG. 1 is a schematic cross-sectional view showing an example of a thermal transfer sheet 100 of the present disclosure. The transfer layer 10 of the first embodiment, as shown in FIG. 1, has a single layer structure consisting of only the molybdenum disulfide-containing layer 3 . Therefore, in the thermal transfer sheet 100 of the present disclosure having the transfer layer 10 of the first form, the molybdenum disulfide-containing layer 3 is positioned on the outermost surface of the printed matter produced by transferring the transfer layer 10 of the first form. . Hereinafter, the molybdenum disulfide-containing layer 3 is meant when the transfer layer 10 of the first embodiment is referred to.

The transfer layer 10 of the first embodiment contains molybdenum disulfide and a binder. The binder contained in the transfer layer 10 of the first embodiment includes vinyl chloride-vinyl acetate copolymer, polyester, acrylic resin, cellulose resin, polyolefin, polyamide, polycarbonate, phenoxy resin, epoxy resin, polystyrene, urethane resin, Examples of resin components include acrylic-modified urethane resins, acrylic-urethane resins such as urethane-modified acrylic resins, resins obtained by modifying these resins with silicone, mixtures of these resins, ionizing radiation-curable resins, and UV-absorbing resins. can. The transfer layer 10 of the first form may contain one kind of binder, or may contain two or more kinds of binders.

Among the above binders, vinyl chloride-vinyl acetate copolymers and polyesters are preferable in that they can impart better abrasion resistance to the transfer layer 10 of the first embodiment, and vinyl chloride-vinyl acetate copolymers are more preferable. preferable.

In addition to this, by using a resin component having a weight average molecular weight (Mw) of 20000 or more as a binder, a synergistic effect with the molybdenum disulfide described above can be used to make the transfer layer 10 of the first embodiment more favorable. Abrasion resistance can be imparted. The weight average molecular weight (Mw) referred to in this specification means the weight average molecular weight in terms of polystyrene, measured by GPC (gel permeation chromatography) according to JIS-K-7252-1 (2008).

Moreover, the transfer layer 10 of the first embodiment may contain optional additives together with molybdenum disulfide and the binder. Examples of optional additives include various fillers such as organic fillers and inorganic fillers that can improve the foil tearability of the transfer layer 10 of the first embodiment. The filler may be powder or sol.

The thickness of the transfer layer 10 of the first embodiment is not limited, and may be determined in consideration of the average particle diameter of molybdenum disulfide, its content, and the like. Specifically, the thickness may be such that molybdenum disulfide does not come off. The thickness of the transfer layer 10 of the first embodiment is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 3 μm or less. By setting the thickness of the transfer layer 10 of the first embodiment to a preferable thickness, it is possible to improve the foil tearability when transferring the transfer layer of the first embodiment.

The method for forming the transfer layer 10 of the first embodiment is not limited, and a molybdenum disulfide-containing layer coating liquid in which molybdenum disulfide, a binder, and optional additives are dispersed or dissolved in an appropriate solvent. is prepared, and this coating liquid can be coated and dried on the substrate 1 or any layer (for example, release layer) provided on the substrate 1. Examples of coating methods include a gravure printing method, a screen printing method, and a reverse coating method using a gravure plate. Other coating methods may also be used. This also applies to methods for applying various coating liquids, which will be described later.

(Transfer layer of the second form)
FIG. 2 is a schematic cross-sectional view showing an example of the thermal transfer sheet 100 of the present disclosure. As shown in FIG. 2, the transfer layer 10 of the second embodiment is formed by laminating a molybdenum disulfide-containing layer 3 and an adhesive layer 7 (also referred to as a heat seal layer) in this order from the substrate 1 side. It has a laminated structure consisting of According to the transfer layer 10 of the second embodiment, the adhesion between the transferred body and the transfer layer 10 can be improved. As the molybdenum disulfide-containing layer 3 in the transfer layer 10 of the second embodiment, the configuration of the transfer layer 10 (molybdenum disulfide-containing layer 3) of the first embodiment described above can be appropriately selected and used.

(adhesive layer)
Components of the adhesive layer 7 include urethane resin, polyolefin such as α-olefin-maleic anhydride, polyester, acrylic resin, epoxy resin, urea resin, melamine resin, phenol resin, polyvinyl acetate, and vinyl chloride-vinyl acetate copolymer. Resin components such as coalescence and cyanoacrylate resins can be exemplified. Moreover, you may use what hardened these components with the hardening|curing agent. Examples of curing agents include isocyanate compounds, aliphatic amines, cycloaliphatic amines, aromatic amines, and acid anhydrides. Also, the adhesive layer 7 may contain molybdenum disulfide.

The thickness of the adhesive layer is preferably 0.5 μm or more and 10 μm or less, more preferably 0.8 μm or more and 2 μm or less. The adhesive layer 7 is prepared by dispersing or dissolving the components exemplified above in an appropriate solvent to prepare an adhesive layer coating liquid, and applying and drying this coating liquid on the molybdenum disulfide-containing layer 3. can be formed by

(Transfer layer of the third form)
FIG. 3 is a schematic cross-sectional view showing an example of the thermal transfer sheet 100 of the present disclosure. As shown in FIG. 3, the transfer layer 10 of the third embodiment has a laminated structure in which a molybdenum disulfide-containing layer 3 and a molten layer 6 are laminated in this order from the substrate 1 side. According to the thermal transfer sheet 100 of the present disclosure having the transfer layer 10 of the third form, the transfer layer 10 of the third form is transferred onto the transfer material in a shape corresponding to the image pattern using a fusion transfer method. As a result, as shown in FIG. 6, the image 30 formed by the melted layer 6 and the molybdenum disulfide-containing layer 3 are laminated in this order on the transfer material 50, and the image formed by the melted layer 6 is formed. 30 and the molybdenum disulfide-containing layer 3 can produce a printed matter 200 having the same planar shape. In other words, it is possible to produce a printed matter 200 in which the molybdenum disulfide-containing layer 3 is positioned only on the image 30 along the planar shape of the image formed by the melted layer 6 . The fusion-type transfer method is an image forming method in which energy corresponding to image information is applied to a thermal transfer sheet, and the transfer layer 10 melted or softened by the application of energy is transferred onto a transfer-receiving material. be. FIG. 6 is a schematic cross-sectional view showing an example of a printed matter 200 produced using the thermal transfer sheet 100 of the present disclosure having the transfer layer of the third embodiment.

As the molybdenum disulfide-containing layer 3 in the transfer layer 10 of the third embodiment, the configuration of the transfer layer 10 (molybdenum disulfide-containing layer 3) of the first embodiment described above can be appropriately selected and used.

The molybdenum disulfide-containing layer 3 contains molybdenum disulfide and has a black color. According to the transfer layer 10 of the third embodiment, as described above, the molybdenum disulfide-containing layer 3 is positioned on the image of the melted layer 6 in the same shape as the image, so the molybdenum disulfide-containing layer 3 has The tint can be canceled by the tint of the image 30 due to the melted layer 6 . In the transfer layer 10 of the third preferred form, the melted layer 6 is a melted layer 6 having a black tint.

The black tint of the molybdenum disulfide-containing layer 3 may be used to impart a design property to printed matter produced by transferring various transfer layers 10 .

(Molten layer)
The melted layer 6 as an example contains a binder and a colorant. Also, the molten layer 6 may contain molybdenum disulfide.

Examples of binders include resin components, wax components, etc. Examples of resin components include ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, polyethylene, polystyrene, polypropylene, polybutene, petroleum resin, and polychloride. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol, vinylidene chloride, acrylic resin, methacrylic resin, polyamide, polycarbonate, fluororesin, polyvinyl formal, polyvinyl butyral, acetylcellulose, nitrocellulose, polyvinyl acetate, polyisobutylene, Examples include ethyl cellulose and polyvinyl acetal. Wax components include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, wood wax, beeswax, whale wax, ivory wax, wool wax, shellac wax, candelilla wax, petrolactam, polyester wax, partially modified Various waxes such as waxes, fatty acid esters and fatty acid amides can be exemplified.

The colorant can be appropriately selected from conventionally known organic or inorganic pigments or dyes. The color of the coloring agent is not limited to yellow, magenta, cyan, and black. For example, as a coloring agent, titanium oxide, zinc oxide, carbon black, iron oxide, iron yellow, ultramarine blue, hologram powder, aluminum powder, metallic pigment, pearl pigment, and the like may be used.

The thickness of the melted layer 6 is preferably 0.5 μm or more and 10 μm. The molten layer 6 is prepared by dispersing or dissolving a binder, a coloring agent, and an additive added as necessary in a suitable solvent to prepare a coating liquid for the molten layer. It can be formed by coating and drying on the molybdenum-containing layer 3 .

Further, a configuration in which an adhesive layer 7 is provided on the melted layer 6 (not shown) may be employed.

Further, in the transfer layer 10 of the various third forms described above, another layer may be provided between the molybdenum disulfide-containing layer 3 and the melted layer 6 (not shown). A protective layer etc. can be illustrated as another layer. Examples of the protective layer include a configuration in which molybdenum disulfide is removed from the molybdenum disulfide-containing layer 3 described in the transfer layer 10 of the first embodiment. In addition, the constitution of the protective layer conventionally known in the field of thermal transfer sheets may be appropriately selected and used.

(Transfer layer of the fourth form)
FIG. 4 is a schematic cross-sectional view showing an example of the thermal transfer sheet 100 of the present disclosure. As shown in FIG. 4, the transfer layer 10 of the fourth embodiment has a laminated structure in which three or more layers are laminated, and the molybdenum disulfide-containing layer 3 is positioned between the layers constituting the transfer layer 10. are doing. The transfer layer 10 of the fourth embodiment shown in FIG. 4 has a laminated structure in which a release layer 4, a molybdenum disulfide-containing layer 3, and a melt layer 6 are laminated in this order from the substrate 1 side. As the molybdenum disulfide-containing layer 3 in the transfer layer 10 of the fourth embodiment, the configuration of the transfer layer 10 (molybdenum disulfide-containing layer 3) of the first embodiment described above can be appropriately selected and used.

According to the transfer layer 10 of the fourth embodiment, by positioning the molybdenum disulfide-containing layer 3 between the layers constituting the transfer layer 10, molybdenum disulfide contained in the molybdenum disulfide-containing layer 3 is suppressed from coming off. can. Further, according to the thermal transfer sheet 100 of the present disclosure having the transfer layer 10 of the fourth embodiment, the abrasion resistance of printed matter produced by transferring the transfer layer 10 of the fourth embodiment can be improved. . Specifically, in the printed matter to be produced, the layer located closer to the surface side of the printed matter than the molybdenum disulfide-containing layer 3 plays a role of protecting the molybdenum disulfide-containing layer 3, and as a result, the The abrasion resistance of the printed matter can be improved.

In the transfer layer 10 of the fourth embodiment, the layer positioned closer to the base material 1 than the molybdenum disulfide-containing layer 3 can be exemplified by a release layer conventionally known in the field of thermal transfer sheets. Also, layers other than this may be positioned. As the peeling layer 4, the molybdenum disulfide-containing layer 3 described in the transfer layer 10 of the first embodiment may be formed by removing molybdenum disulfide. Moreover, two or more layers constituting the transfer layer 10 may be positioned closer to the substrate 1 than the molybdenum disulfide-containing layer 3 .

In the transfer layer 10 of the fourth embodiment, the layer positioned above the molybdenum disulfide-containing layer 3 when the molybdenum disulfide-containing layer 3 is on top and the substrate 1 is on the bottom is exemplified above. Examples include the melting layer 6, the adhesive layer 7, the receiving layer 5 to be described later, and the like. Also, layers other than this may be positioned.

Further, the molybdenum disulfide-containing layer 3 may contain molybdenum disulfide in a layer located closer to the substrate and a layer located on the opposite side.

(Transfer layer of the fifth form)
FIG. 5 is a schematic cross-sectional view showing an example of the thermal transfer sheet 100 of the present disclosure. As shown in FIG. 5, the transfer layer 10 of the fifth embodiment has a laminated structure in which a molybdenum disulfide-containing layer 3 and a receiving layer 5 are laminated in this order from the substrate 1 side. As the molybdenum disulfide-containing layer 3 in the transfer layer 10 of the fifth embodiment, the configuration of the transfer layer 10 (molybdenum disulfide-containing layer 3) of the first embodiment described above can be appropriately selected and used.

According to the thermal transfer sheet 100 of the present disclosure having the transfer layer 10 of the fifth form, as shown in FIG. 7A, the thermal transfer image 35 is formed on the receiving layer 5 of the fifth form, and then As shown in b), the transfer layer 10 of the fifth form is transferred onto the transferred material, and the transfer layer 10 is peeled off from the base material 1 side, thereby forming the transfer layer 10 as shown in FIG. 7(c). A printed matter 200 can be manufactured in which the receiving layer 5 having the thermally transferred image 35 formed thereon and the molybdenum disulfide-containing layer 3 are laminated in this order on the transfer member 50 . A thermal transfer sheet 100 of the present disclosure having a transfer layer 10 of the fifth form serves as an intermediate transfer medium. FIGS. 7A _to 7C are schematic process diagrams showing an example of a method for producing a printed matter using the thermal transfer sheet 100 of the present disclosure having the transfer layer 10 of the fifth embodiment.

(receptive layer)
Components of the receptor layer 5 include polyolefins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, and polyacrylic acid. Vinyl resins such as esters, polyesters such as polyethylene terephthalate and polybutylene terephthalate, copolymers of olefin monomers such as polystyrene, polyamide, ethylene and propylene with other vinyl polymers, ionomers, cellulose resins such as cellulose diastase, polycarbonates, etc. I can give an example.

The thickness of the receiving layer 5 is preferably 1 μm or more and 10 μm or less. For the receiving layer 5, a receiving layer coating liquid is prepared by dispersing or dissolving the above-exemplified components in an appropriate solvent, and this coating liquid is used as the molybdenum disulfide-containing layer 3 or the molybdenum disulfide-containing layer. It can be formed by coating and drying on any layer provided on the layer 3 .

An optional layer such as an intermediate layer may be provided between the molybdenum disulfide-containing layer 3 and the receiving layer 5 . Also, an adhesive layer 7 may be provided on the receiving layer 5 .

Various forms including the molybdenum disulfide-containing layer 3 have been described above as the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure. A configuration in which the configurations of the layers 10 are appropriately combined may be employed. Also, molybdenum disulfide may be contained in all layers constituting the transfer layer 10 .

(release layer)
A release layer may be provided between the substrate 1 and the transfer layer 10 (not shown). By providing the release layer, the transferability of the transfer layer 10 from the substrate 1 side can be improved. Components of the release layer include waxes, silicone waxes, silicone resins, various silicone-modified resins such as silicone-modified acrylic resins, fluororesins, fluorine-modified resins, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymers, acrylic resins, Examples include thermally crosslinkable epoxy-amino copolymers, thermally crosslinkable alkyd-amino copolymers, melamine resins, cellulose resins, urea resins, polyolefins, cellulose resins, polyamides, lactic acid resins, and the like. The release layer may contain one component alone, or may contain two or more components. As an example, the thickness of the release layer is 0.1 μm or more and 1 μm or less.

When the optionally provided release layer is in direct contact with the molybdenum disulfide-containing layer 3, the release layer contains, as a main component, a component different from the main binder contained in the molybdenum disulfide-containing layer 3. preferably contained. For example, when the release layer contains a resin as a main component and the molybdenum disulfide-containing layer 3 contains a resin as a main binder, the main monomer ( It is preferable that the main monomer constituting the main resin (main binder) contained in the molybdenum disulfide-containing layer 3 is different from the main monomer. For example, when the molybdenum disulfide-containing layer 3 contains polyester as the main binder, the release layer contains acrylic resin, vinyl chloride-vinyl acetate copolymer, cellulose resin, etc. as the main component. there is

(back layer)
Also, a back layer may be provided on the surface of the substrate 1 opposite to the surface on which the transfer layer 10 is located (not shown).

Components of the back layer include polyester, polyacrylate, polyvinyl acetate, acrylic-styrene copolymer, urethane resin, polyolefin such as polyethylene and polypropylene, polystyrene, polyvinyl chloride, polyether, polyamide, polyimide, and polyamideimide. , polycarbonate, polyacrylamide, polyvinyl chloride, polyvinyl acetals such as polyvinyl acetal and polyvinyl butyral, and resin components such as silicone modified products thereof. Among them, polyamideimide or its silicone modified product can be preferably used from the viewpoint of heat resistance and the like.

In addition, for the purpose of improving the slip property, the back layer may contain wax, higher fatty acid amide, phosphoric acid ester compound, metal soap, silicone oil, release agent such as surfactant, organic powder such as fluororesin, silica, clay, etc. , talc, and inorganic particles such as calcium carbonate.

For the back layer, for example, a back layer coating liquid is prepared by dispersing or dissolving the above components and various additives added as necessary in an appropriate solvent, and this coating liquid is applied to the base material. 1 by coating and drying. The thickness of the back layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.3 μm or more and 2 μm or less.

(colorant layer)
Further, a coloring material layer may be provided on the substrate 1 in a plane-sequential manner with the transfer layer 10 (not shown). A coloring material layer as an example contains a sublimation dye as a coloring material and a binder. According to the thermal transfer sheet 100 of the present disclosure having a color material layer, when a thermal transfer image receiving sheet having a receiving layer is used as a transfer material, a thermal transfer image is formed on the receiving layer, and the thermal transfer image is formed. The transfer of the transfer layer 10 onto the coated receiving layer can be done with one thermal transfer sheet. As the colorant layer, conventionally known colorant layers in the field of thermal transfer sheets can be appropriately selected and used. Further, a melt-type coloring material layer can also be used as the coloring material layer.

The material to be transferred 50 onto which the transfer layer 10 of the thermal transfer sheet 100 of the present disclosure is transferred is mainly composed of plain paper, fine paper, tracing paper, plastic film, vinyl chloride, vinyl chloride-vinyl acetate copolymer, and polycarbonate. A configured plastic card or the like can be exemplified. Also, a material having a predetermined image can be used as the material to be transferred. A thermal transfer image receiving sheet can also be used as the transfer material. Moreover, you may use the transfer-receiving body other than this.

For the transfer of the transfer layer 10 onto the object to be transferred, for example, a method using a heating device such as a thermal head, a hot stamp method, a heat roll method, or the like can be used. Also, other methods can be used.

In the specification of the present application, the resins and the like constituting each layer are exemplified, but these resins may be homopolymers of the monomers constituting each resin. It may be a copolymer of a main component monomer and one or more other monomers, or a derivative thereof. For example, in the case of an acrylic resin, it may contain acrylic acid or methacrylic acid monomers or acrylic acid ester or methacrylic acid ester monomers as main components. Modified products of these resins may also be used. Resins other than those exemplified herein may also be used.

EXAMPLES Next, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, parts and % are based on mass unless otherwise specified.

(Example 1)
A PET (polyethylene terephthalate) film having a thickness of 4.5 μm was used as a substrate, and a release layer coating liquid 1 having the following composition was applied and dried on one side of the substrate to obtain a thickness of 2 μm. to form a release layer. Next, a melt layer coating liquid having the following composition was applied onto the release layer and dried to form a melt layer having a thickness of 1 μm. On the other side of the substrate, a back layer coating liquid having the following composition is applied and dried to form a back layer having a thickness of 1 μm, thereby forming a release layer on one side of the substrate. , the melted layer were laminated in this order, and a back layer was provided on the other side to obtain the thermal transfer sheet of Example 1. The release layer and the melting layer constitute the transfer layer of the thermal transfer sheet of the present disclosure. In the thermal transfer sheet of Example 1, the release layer corresponds to the molybdenum disulfide-containing layer.

<Coating solution for back layer>
・ Polyvinyl butyral 70 parts (Slec (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
・ Polyisocyanate curing agent 15 parts (Takenate (registered trademark) D218 Mitsui Chemicals, Inc.)
・ Phosphate ester 15 parts (Plysurf (registered trademark) A208S Daiichi Kogyo Seiyaku Co., Ltd.)
・Methyl ethyl ketone 300 parts ・Toluene 300 parts

<Coating liquid 1 for release layer>
・ Acrylic resin (binder (A)) 95 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Co., Ltd.)
・ Molybdenum disulfide average particle size: 0.45 μm (particles (A)) 5 parts (M-5 Daizo Co., Ltd.)
・200 parts of toluene ・200 parts of methyl ethyl ketone

<Coating liquid for molten layer>
- Carbon black dispersion (solid content 46%) 53 parts (40 parts of carbon black, 6 parts of dispersant, 27 parts of methyl ethyl ketone, 27 parts of toluene)
・ Acrylic resin 37 parts (Dianal (registered trademark) BR-83 Mitsubishi Chemical Corporation)
・Vinyl chloride-vinyl acetate copolymer 10 parts (Solbin (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
・Methyl ethyl ketone 140 parts ・Toluene 140 parts

(Examples 2 to 25, Comparative Examples 1 to 18)
Examples 2 to 25 were prepared in the same manner as in Example 1, except that the release layer coating solution 1 was changed to the release layer coating solutions 2 to 25 shown in Table 1 below to form the release layer. A thermal transfer sheet was obtained. Comparative Examples 1 to 1 were carried out in the same manner as in Example 1, except that the release layer coating solutions A to R shown in Table 2 below were used to form the release layers. 18 thermal transfer sheets were obtained. Table 3 shows the details of the binder and particles contained in each coating liquid in Tables 1 and 2. In addition, in all of the peeling layer coating liquids, the solvent and its compounding amount are the same as in the peeling layer coating liquid 1. In the thermal transfer sheets of Examples 2-25 and Comparative Examples 1-18, the release layer corresponds to the molybdenum disulfide-containing layer.

(Example 26)
A PET (polyethylene terephthalate) film with a thickness of 4.5 μm is used as a substrate, and the release layer coating liquid 11 having the above composition is applied and dried on one side of the substrate to obtain a thickness of 1 μm. to form a release layer. Next, a protective layer coating liquid 1 having the following composition was applied onto the release layer and dried to form a protective layer having a thickness of 1 μm. Next, the melted layer coating solution having the composition described above was applied onto the protective layer and dried to form a melted layer having a thickness of 1 μm. Further, a back layer coating liquid is applied onto the other surface of the substrate and dried to form a back layer having a thickness of 1 μm, thereby forming a release layer and a protective layer on one surface of the substrate. , the melted layer were laminated in this order, and a backing layer was provided on the other side to obtain the thermal transfer sheet of Example 26. The release layer, protective layer, and melting layer constitute the transfer layer of the thermal transfer sheet of the present disclosure. In the thermal transfer sheet of Example 26, the release layer corresponds to the molybdenum disulfide-containing layer.

<Protective layer coating solution 1>
・ Acrylic resin 100 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Co., Ltd.)
・200 parts of toluene ・200 parts of methyl ethyl ketone

(Example 27)
The release layer coating solution 11 was changed to the release layer coating solution A having the above composition to form a release layer, and the protective layer coating solution 1 was changed to the protective layer coating solution 2 having the following composition. In the same manner as in Example 26, except that the protective layer was formed by using got a sheet. In the thermal transfer sheet of Example 27, the protective layer corresponds to the molybdenum disulfide-containing layer.

<Protective layer coating solution 2>
・ Acrylic resin 80 parts (Dianal (registered trademark) BR-87 Mitsubishi Chemical Co., Ltd.)
・ Molybdenum disulfide (average particle size: 1.2 μm) 20 parts (C powder Daizo Co., Ltd.)
・200 parts of toluene ・200 parts of methyl ethyl ketone

(Comparative Example 19)
A release layer and a protective layer were formed on the substrate in the same manner as in Example 26, except that the release layer coating solution A having the above composition was used instead of the release layer coating solution 11. , and the thermal transfer sheet of Comparative Example 19 provided with a transfer layer in which the melted layers are laminated in this order.

(Manufacture of prints)
A polyvinyl chloride card (PVC card) (Dai Nippon Printing Co., Ltd.) was used as a transfer medium. The transfer layer was transferred to the thermal transfer sheet of each example and comparative example under the following conditions, and a printed material in which the transfer layer of the thermal transfer sheet of each example and comparative example was transferred onto a transfer material was obtained. Obtained.

(test printer)
・Thermal head: KEE-57-12GAN2-STA (Kyocera Corporation)
・ Heating element average resistance value: 3303 (Ω)
・Main scanning direction print density: 300 (dpi)
・Sub-scanning direction print density: 300 (dpi)
・Line cycle: 3 (msec./line)
・Print start temperature: 35 (°C)
・Pulse duty ratio: 85 (%)
・Applied voltage: 20 (V)
・Image pattern: Black solid image (0/255 image gradation)

(Abrasion resistance evaluation)
The printed matter of each of the examples and comparative examples produced above was subjected to the Taber test method in accordance with ANSI-INCITS 322-2002, 5.9 Surface Abrasion using a Taber tester, using an abrasion wheel CS-10F, a load of 500 gf, 60 cycles/min. A wear test was performed at Every 100 cycles, the reflection density of the worn portion was measured with RD918 (X-Rite), and the abrasion was terminated when the density became less than 80% of the density before abrasion. Table 4 shows the number of cycles at which the reflection density became less than 80% of the density before abrasion.

1: Substrate 3: Layer containing molybdenum disulfide (molybdenum disulfide-containing layer)
4 Peeling layer 5 Receiving layer 6 Melting layer 7 Adhesive layer 10 Transfer layer 100 Thermal transfer sheet 50 Material to be transferred 200 print

Claims (4)

A thermal transfer sheet comprising a substrate and a transfer layer provided on the substrate,
The transfer layer is provided so as to be peelable from the base material side,
The transfer layer exhibits a laminated structure including a melted layer,
Among the layers constituting the transfer layer, the layer located closer to the substrate than the melted layer contains a binder and molybdenum disulfide.
Thermal transfer sheet. A thermal transfer sheet comprising a substrate and a transfer layer provided on the substrate,
The transfer layer is provided so as to be peelable from the base material side,
The transfer layer exhibits a laminated structure including a receiving layer,
Among the layers constituting the transfer layer, the layer located closer to the substrate than the receiving layer contains a binder and molybdenum disulfide.
Thermal transfer sheet. The transfer layer has a laminated structure in which three or more layers are laminated,
a layer containing the binder and molybdenum disulfide is located between layers constituting the transfer layer;
The thermal transfer sheet according to claim 1 or 2. A coloring material layer is provided on the base material in a plane-sequential manner with the transfer layer,
The thermal transfer sheet according to claim 1 or 2.

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