JP7380035B2 - Decorative sheet manufacturing method, decorative article manufacturing method, and decorative sheet - Google Patents

Description

The present invention relates to a method for manufacturing a decorative sheet, a method for manufacturing a decorative article, and a decorative sheet.

2. Description of the Related Art Recently, attempts have been made to decorate arbitrary objects with thermal transfer images, and as one example, a method of decorating objects using an intermediate transfer medium has been proposed. This method uses an intermediate transfer medium provided with a transfer layer including a receptor layer on a base material, and after forming a thermal transfer image on the receptor layer located on the outermost surface of the intermediate transfer medium, transfers the image to an arbitrary object. , an intermediate transfer medium on which a thermally transferred image is formed is placed on top of the intermediate transfer medium, and thermal energy is applied from the intermediate transfer medium side to transfer the transfer layer, including the receiving layer on which the thermally transferred image is formed, onto an arbitrary object. It is something.

However, the method using an intermediate transfer medium is not suitable for objects that are easily damaged by applying thermal energy. Under these circumstances, Patent Document 1 proposes a transfer sheet in which a water-permeable support, a water-soluble glue, and a transfer layer are laminated in this order. According to the transfer sheet proposed in Patent Document 1, the transfer layer can be transferred even to heat-sensitive materials by dissolving the water-soluble glue with water.

Japanese Patent Application Publication No. 11-59092

The present invention has been made in view of the above situation, and provides a method for manufacturing a decorative sheet that can easily produce a decorative article with a design, and a method for manufacturing a decorative sheet that can easily produce a decorative article with a design. The main objective is to provide a method for manufacturing ornaments that can be easily manufactured.

A method for manufacturing a decorative sheet according to an embodiment of the present disclosure to solve the above problems includes a thermal transfer image-receiving sheet in which a receptor layer is provided on a support, and a thermal transfer sheet in which a dye layer is provided on a base material. a step of transferring a sublimable dye contained in the dye layer to the receptor layer to form a thermally transferred image on the receptor layer; and forming an aqueous adhesive layer on the receptor layer on which the thermally transferred image is formed. The step of forming the aqueous adhesive layer includes forming the aqueous adhesive layer by transfer, wherein the aqueous adhesive layer increases or develops adhesiveness due to water absorption, and the step of forming the aqueous adhesive layer includes forming the aqueous adhesive layer by transfer. a step of forming the thermal transfer image using the thermal transfer sheet, the thermal transfer sheet having the dye layer and the water-based adhesive layer provided on the base material in a plane-sequential manner; , and forming the aqueous adhesive layer.
In the above method for producing a decorative sheet, the receptor layer may contain a component having a hydroxyl group.
In the above method for producing a decorative sheet, the receiving layer and the aqueous adhesive layer both contain a component having a hydroxyl group, and in the step of forming the aqueous adhesive layer, the receiving layer on which the thermal transfer image is formed is The aqueous adhesive layer may be formed such that the layer and the aqueous adhesive layer are in direct contact with each other.
A method for producing a decorative sheet according to one embodiment is to combine a thermal transfer image-receiving sheet having a receiving layer provided on a support and a thermal transfer sheet having a dye layer provided on a base material, and to remove the sublimation contained in the dye layer. forming a thermally transferred image on the receptor layer by transferring a color dye to the receptor layer; and forming an aqueous adhesive layer on the receptor layer on which the thermally transferred image is formed, wherein the aqueous adhesive layer is , the adhesiveness increases due to water absorption, or the adhesiveness develops due to water absorption.

Further, in the method for producing the decorative sheet, a separation auxiliary layer is provided between the support and the receptor layer of the thermal transfer image-receiving sheet, and the surface of the separation auxiliary layer on the receptor layer side is the upper surface. Additionally, a thermal transfer image-receiving sheet may be used in which the receptor layer can be separated using the upper surface of the separation auxiliary layer as a separation interface.

Further, the method for manufacturing the decorative sheet described above may use a thermal transfer image-receiving sheet in which a durable layer is provided between the separation auxiliary layer and the receptor layer.

Moreover, in the method for manufacturing the decorative sheet described above, the step of forming the aqueous adhesive layer may be a step of forming the aqueous adhesive layer by transfer.

Further, in the above-described method for producing a decorative sheet, the thermal transfer sheet has the dye layer and the water-based adhesive layer provided on the base material in a plane-sequential manner, and using the thermal transfer sheet, the A step of forming a thermal transfer image and a step of forming the aqueous adhesive layer may be performed.

Further, the method for manufacturing the decorative sheet described above may use a thermal transfer sheet in which a heat-sealing layer is provided on the aqueous adhesive layer. Moreover, this heat-sealing layer may contain a coloring agent.

Further, a method for manufacturing a decorative article according to an embodiment of the present disclosure for solving the above problems includes a step of integrating a decorative object and a decorative sheet, and the decorative sheet is manufactured by the above manufacturing method. Using the manufactured decorative sheet, the decorative object and the decorative sheet are integrated using water.

Further, in order to solve the above problems, the method for manufacturing a decorative article according to an embodiment of the present disclosure includes, on a decorative object, a water-based adhesive layer whose adhesiveness increases due to water absorption or whose adhesiveness develops due to water absorption. Before or after the forming step and the step of forming the aqueous adhesive layer, a thermal transfer image-receiving sheet having a receiving layer provided on a support, and a dye layer containing a sublimable dye provided on the base material. a step of combining a thermal transfer sheet and transferring the sublimable dye contained in the dye layer to the receiving layer to prepare an image-formed product in which a thermal transfer image is formed on the receiving layer; and using water. , a step of integrating the decoration object on which the aqueous adhesive layer is formed and the image-formed object.

Further, in a decorative sheet according to an embodiment of the present disclosure for solving the above problems, an aqueous adhesive layer is provided on an image-formed product having an image, and the adhesiveness of the aqueous adhesive layer increases due to water absorption. , or one that develops tackiness due to water absorption.

According to the method for manufacturing a decorative sheet and the decorative sheet according to the embodiments of the present disclosure, it is possible to easily manufacture a decorative article with design. Further, according to the method for manufacturing a decorative article according to an embodiment of the present disclosure, a decorative article having a design can be easily manufactured.

(a) to (d) are process diagrams showing an example of a method for manufacturing a decorative sheet according to an embodiment of the present disclosure. (a) to (d) are process diagrams showing an example of a method for manufacturing a decorative sheet according to an embodiment of the present disclosure. (a) to (c) are schematic cross-sectional views showing an example of a thermal transfer image-receiving sheet used for manufacturing a decorative sheet according to an embodiment of the present disclosure. (a) and (b) show an example of the state when the support is separated after the decorative sheet manufactured by the method for manufacturing a decorative sheet according to the embodiment of the present disclosure is pasted on a decoration object. It is a schematic sectional view. (a) and (b) are schematic cross-sectional views showing an example of a thermal transfer sheet used for manufacturing a decorative sheet according to an embodiment of the present disclosure. (a) to (c) are schematic cross-sectional views showing an example of a decorative sheet manufactured by the method for manufacturing a decorative sheet according to an embodiment of the present disclosure.

<<Method for manufacturing decorative sheets>>
Hereinafter, a method for manufacturing a decorative sheet according to an embodiment of the present disclosure (hereinafter referred to as a method for manufacturing a decorative sheet of the present disclosure) will be described. 1(a) to (d) and FIG. 2(a) to (d) are process diagrams showing an example of the method for manufacturing a decorative sheet of the present disclosure. In the process diagram shown in FIG. , a thermal transfer sheet 10 is used in which a dye layer 3 and an aqueous adhesive layer 4 are sequentially provided on the same side of a substrate 1, and a receptor layer 80 is provided on a support 50 as a thermal transfer image-receiving sheet 100. A thermal transfer image-receiving sheet 100 is used. In the process diagram shown in FIG. 2, as a thermal transfer sheet 10, a dye layer 3 and an aqueous adhesive layer 4 are provided in sequence on the same side of a base material 1, and a heat seal layer 5 is further provided on the aqueous adhesive layer 4. The thermal transfer image-receiving sheet 100 is a thermal transfer image-receiving sheet 100 in which a separation auxiliary layer 70, a durable layer 60, and a receptor layer 80 are laminated in this order on a support 50. The thermal transfer sheet 10 and the thermal transfer image-receiving sheet 100 used in the decorative sheet manufacturing method of the present disclosure are not limited to those shown in the process diagrams of FIGS. 1 and 2, but are The sheet 10 and the thermal transfer image-receiving sheet 100 can be used in appropriate combination. Further, a part of the structure may be removed from the thermal transfer sheet or thermal transfer image-receiving sheet shown in each figure.

The decorative sheet manufacturing method of the present disclosure includes a step of forming a thermal transfer image and a step of forming an aqueous adhesive layer. Each step will be explained below.

<Step of forming a thermal transfer image>
In this step, as shown in FIGS. 1(a) and 2(a), a thermal transfer image receiving sheet 100 having a receiving layer 80 provided on a support 50 and a dye layer 3 provided on a base material 1 are prepared. The thermal transfer sheets 10 are combined, and the sublimable dye contained in the dye layer 3 is transferred to the receptor layer 80 of the thermal transfer image-receiving sheet 100 to form a thermal transfer image, as shown in FIGS. 1(b) and 2(b). This is the process of forming. Hereinafter, a product in which a thermal transfer image is formed on the receptor layer 80 of the thermal transfer image-receiving sheet 100 may be referred to as an image-formed product. In addition, in FIGS. 1 and 2, the thermal transfer sheet 10 provided with a single dye layer 3 is used as the dye layer 3, but as shown in FIGS. A plurality of dye layers 3, for example, a yellow dye layer 3Y containing a yellow sublimable dye, a magenta dye layer 3M containing a magenta sublimable dye, and a cyan dye layer 3C containing a cyan sublimable dye are attached to the base material. Thermal transfer sheets 10 may be provided in a sequential manner on the same surface of the thermal transfer sheet 10. Further, the dye layer 3 may contain a sublimable dye other than this. In addition, one or more of a black molten ink layer, a fluorescent layer, a heat seal layer, etc. may be further provided in a plane-sequential manner.

The thermal transfer image is produced by overlapping the thermal transfer image-receiving sheet 100 and the thermal transfer sheet 10 having a dye layer, and applying energy to the thermal transfer sheet using a heating means such as a thermal head in the printer to sublimate the dye layer 3. It can be formed by diffusing and transferring a coloring dye into the receiving layer 80.

<Step of forming a water-based adhesive layer>
This step is a step of forming an aqueous adhesive layer 4 on the image-formed product, the adhesiveness of which increases or develops by absorbing water.

As an example, the aqueous adhesive layer is formed using a thermal transfer sheet 10 in which a single-layer or laminated transfer layer including the aqueous adhesive layer 4 is provided on the base material 1, and a thermal transfer image-receiving sheet on which a thermal transfer image is formed. It is formed by transfer onto the receptor layer 80 of 100. When the transfer layer has a laminated structure including the aqueous adhesive layer 4, the aqueous adhesive layer 4 is located closest to the base material 1 among the layers constituting the transfer layer. Thereby, when the transfer layer is transferred, the aqueous adhesive layer 4 can be positioned on the outermost surface. Note that, as described later, the protective layer may be positioned closest to the base material 1 among the layers constituting the transfer layer, and the protective layer may be positioned on the outermost surface when the transfer layer is transferred. Through this step, a decorative sheet 200 is obtained in which the water-based adhesive layer 4 is provided on the receptor layer 80 of the thermal transfer image-receiving sheet 100, as shown in FIGS. 1(d) and 2(d).

As shown in FIGS. 1(c) and 2(c), the aqueous adhesive layer 4 is formed by overlapping a thermal transfer image-receiving sheet 100 with a thermal transfer image formed on the receiving layer 80 and a thermal transfer sheet 10 having the aqueous adhesive layer 4. At the same time, energy is applied to this thermal transfer sheet to bring the aqueous adhesive layer 4 (heat seal layer 5 in the form shown in FIG. 2) into close contact (adhesion, melting, Transfer can be performed by peeling off the aqueous adhesive layer 4 from the base material 1 side.

As another example, the aqueous adhesive layer is formed by pasting the aqueous adhesive layer 4 in the form of a film or sheet onto an image-formed object using an adhesive layer (which may be an adhesive film or an adhesive sheet). form.

According to the method for manufacturing a decorative sheet of the present disclosure, by forming a thermal transfer image using a dye layer containing a sublimable dye, the formed thermal transfer image can have high definition. Further, by forming an aqueous adhesive layer 4 on the image formed object, a decorative sheet 200 is obtained in which the aqueous adhesive layer 4 is provided on the image formed object on which a high-definition thermal transfer image is formed. As shown in FIG. 1(d) and FIG. 2(d), on the outermost surface of the obtained decorative sheet 200, an aqueous adhesive layer 4 whose adhesiveness increases or develops adhesiveness due to water absorption is located. Therefore, the decorative object 300 and the decorative sheet 200 can be bonded together by simply allowing the water-based adhesive layer 4 of the manufactured decorative sheet 200 to absorb water (see FIG. 6). In other words, the decoration object 300 and the decoration sheet 200 can be integrated. In other words, the decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure is used to easily decorate the decorative object 300 (sometimes referred to as the decorative object 300). (In some cases, it is possible.)

Furthermore, the decorative sheet manufactured by the method for manufacturing a decorative sheet of the present disclosure can be bonded with water and does not require heat to be bonded to a decorative object, so that when the decorative sheet manufactured is made thinner. However, no deformation due to heat occurs. In other words, the quality of decorative items manufactured using the decorative sheet can be improved. In addition, it is possible to bond decorative objects that are sensitive to heat, increasing the degree of freedom in selecting decorative objects.

Note that the decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure only needs to have the aqueous adhesive layer 4 located on the outermost surface at the time of being bonded to the decoration object. In other words, at a stage before being attached to a decorative object, for example, during storage of the decorative sheet 200, another layer that can be removed (separated) from the aqueous adhesive layer 4 is located on the aqueous adhesive layer 4. Good too. As such a layer, a protective layer (which may be a protective film or the like) for the purpose of protecting the aqueous adhesive layer 4 can be exemplified. As an example, the method for manufacturing a decorative sheet of the present disclosure includes a step of forming a protective layer on the aqueous adhesive layer 4 after or together with the formation of the aqueous adhesive layer 4. Examples of the protective layer include a release film, a separate paper, a separate film, a release film, a release paper, a release layer, and the like. For example, when forming the aqueous adhesive layer 4 by transfer, by transferring the transfer layer including the protective layer, the aqueous adhesive layer 4, and the heat seal layer, the protective layer can be formed at the same time as the aqueous adhesive layer 4. A decorative sheet 200 having a protective layer on the outermost surface can be obtained.

Hereinafter, each step in the decorative sheet manufacturing method of the present disclosure and an example of the thermal transfer sheet 10 and thermal transfer image-receiving sheet 100 that can be used in the decorative sheet manufacturing method of the present disclosure will be described in more detail.

(Thermal transfer image receiving sheet)
The thermal transfer image-receiving sheet 100 used in the decorative sheet manufacturing method of the present disclosure has a structure in which a receiving layer 80 is provided on a support 50, as shown in FIG. 3(a). Moreover, as shown in FIGS. 3(b) and 3(c), an arbitrary layer may be provided between the support 50 and the receiving layer 80.

(Support)
The support 50 may be anything that can support the receptor layer 80, and may have a single layer structure or a laminated structure. The support body 50 as an example has a laminated structure including a plurality of base materials. When the support body 50 has a laminated structure including a plurality of base materials, these base materials may be the same, or different base materials may be combined. For example, the support 50 may include a paper base material and a film base material. Note that the support body 50 shown in FIGS. 3(a) to 3(c) has a single-layer structure.

Examples of the base material constituting the support body 50 include a paper base material, a film base material (sometimes referred to as a resin base material or a resin sheet), and the like. Paper base materials include high quality paper, coated paper, resin coated paper, art paper, cast coated paper, paperboard, synthetic paper (polyolefin type, polystyrene type), synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin. Examples include internal paper, cellulose fiber paper, and the like. Examples of the film base material include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins, polyvinyl chloride, polymethacrylates, polypropylene, polycarbonates, cellulose acetate, polyethylene derivatives, polyamides, and polymethylpentene. These film base materials may be stretched or unstretched. The film base material may be a transparent film base material or an opaque film base material. Further, the film base material may be a white film base material containing a white pigment or a filler. Moreover, a film base material having microvoids inside may be used. The thickness of the support is not particularly limited, and is preferably 10 μm or more and 300 μm or less.

When the support 50 has a laminated structure including a film base material as described above, the film base material laminated on the receiving layer 80 side is preferably a film base material having voids. Examples of film base materials with voids include those manufactured by kneading inorganic fine particles into a polymer and creating voids using the inorganic fine particles as cores when stretching the compound, and those manufactured by kneading inorganic fine particles into a polymer and creating voids with the inorganic fine particles as cores when stretching the compound, and An example is a compound produced by blending incompatible polymers (one or more types). When this compound is viewed microscopically, the polymers form a fine sea-island structure, and when the compound is stretched, voids occur due to separation at the sea-island interface or large deformation of the polymer forming the islands. The thickness of the film base material having the above-mentioned microvoids is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 50 μm or less.

Moreover, instead of forming the support 50 into a laminated structure, or in addition to this, a heat insulating layer may be provided between the support 50 and the receiving layer 80 (not shown). As the heat insulating layer, any heat insulating layer conventionally known in the field of thermal transfer image-receiving sheets can be appropriately selected and used.

Further, when the support body 50 has a laminated structure including a plurality of base materials, an adhesive layer may be provided between the base materials. The adhesive layer for bonding the base materials together contains an adhesive and has an adhesive function. Examples of adhesive components include polyurethane, polyolefin, polyester, acrylic resin, epoxy resin, urea resin, melamine resin, phenol resin, vinyl acetate, and cyanoacrylate. Further, these adhesive components may be cured with a curing agent. Examples of the curing agent include isocyanate compounds, aliphatic amines, cycloaliphatic amines, aromatic amines, and acid anhydrides. The thickness of the adhesive layer is preferably 2 μm or more and 10 μm or less.

Furthermore, instead of bonding the base material and the film using the adhesive layer described above, the base materials, for example, a paper base material and a film base material, may be bonded together by EC sand lamination using polyethylene or the like. .

(receptive layer)
As shown in FIGS. 3A to 3C, a receptor layer 80 is provided on the support 50 of the thermal transfer image-receiving sheet, either directly or indirectly through another layer. The receiving layer 80 contains a component capable of receiving sublimable dyes. Components that can accept sublimable dyes include acrylic resin, polyolefin, polyvinyl chloride, or halogenated resin such as polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, and ethylene-vinyl acetate copolymer. , or vinyl resins such as polyacrylic acid esters, polyesters such as polyethylene terephthalate or polybutylene terephthalate, copolymers of olefins such as polystyrene, polyamide, ethylene, or propylene with other vinyl polymers, polycarbonates, cellulose resins, etc. I can give an example. The receiving layer 80 may contain one type of component capable of receiving sublimable dyes, or may contain two or more types of components capable of receiving sublimable dyes.

There is no limitation on the weight of the component capable of receiving sublimable dyes based on the total weight of the receiving layer 80, but it is preferably 50% by weight or more.

Among these components, vinyl chloride-vinyl acetate copolymer and acrylic resin are preferred components since they can form thermal transfer images with high density.

Further, the receiving layer 80 preferably contains a resin component having a hydroxyl group, and more preferably contains a vinyl chloride-vinyl acetate copolymer having a hydroxyl group. According to the receptive layer 80 of this form, a layer that is transferred onto the receptive layer 80 in the step of transferring the aqueous adhesive layer 4 and that is in direct contact with the receptive layer 80 (in the form shown in FIG. 5A, the aqueous adhesive layer 4. In the form shown in FIG. 5(b), the adhesion between the receptor layer 80 and the layer in contact with the receptor layer 80 is good, provided that the heat seal layer 5) also contains a resin component having a hydroxyl group. It can be done. As a result, when the aqueous adhesive layer 4 of the decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure absorbs water, the adhesion between the receptor layer 80 and the layer in contact with the receptor layer 80 is improved due to the influence of water. decreases, and it is possible to suppress the occurrence of unintended separation at this interface.

The receiving layer 80 may be made of solid waxes such as polyethylene wax, amide wax, Teflon (registered trademark) powder, fluorine-based or phosphate ester-based surfactants, silicone oil, reactive silicone oil, curable silicone oil, etc. It may contain various modified silicone oils, mold release agents such as various silicone resins, various fillers, various antistatic agents, etc.

Although there is no particular limitation on the thickness of the receiving layer 80, it is preferably 0.3 μm or more and 10 μm or less. There are no limitations on the method for forming the receptor layer 80, and a coating solution for the receptor layer is prepared by dispersing or dissolving components capable of receiving sublimable dyes and optional additives added as necessary in an appropriate solvent. However, this coating liquid can be applied and dried on the support 50 or any layer provided on the support 50 (for example, a separation auxiliary layer 70 or a durable layer 60, which will be described later). Examples of methods for applying the receptor layer coating solution include gravure printing, screen printing, and reverse coating using a gravure plate. Moreover, other coating methods can also be used. This also applies to the coating methods of various coating liquids described below.

(Separation auxiliary layer)
As shown in FIG. 3(b), a thermal transfer image-receiving sheet 100 as an example used in the method for manufacturing a decorative sheet of the present disclosure includes a separation auxiliary layer 70 between a support 50 and a receptor layer 80 for separation. When the surface of the auxiliary layer on the receiving layer 80 side is the top surface, a part of the thermal transfer image-receiving sheet can be separated using the top surface of the separation auxiliary layer 70 as a separation interface.

According to the thermal transfer image-receiving sheet 100 having such a separation auxiliary layer 70, the degree of freedom in selecting the support 50 of the thermal transfer image-receiving sheet 100 can be increased. Specifically, by having a configuration in which the support body 50 can be separated, no consideration is required for the support body 50, and the degree of freedom in selecting the support body 50 can be increased. For example, if the support 50 of the thermal transfer image-receiving sheet 100 is a paper base material or an opaque film base material, the thermal transfer image formed on the receptor layer 80 cannot be seen from the support 50 side, or the visibility of the thermal transfer image is poor. When using one that lowers the height, the support 50 may be separated in the end. On the other hand, when the support 50 includes a paper base material or an opaque film base material, before the support 50 is separated, the decorative sheet manufactured by the decorative sheet manufacturing method of the present disclosure is The outer edge can be accurately grasped, and the manufactured decorative sheet and the decorative object can be easily aligned.

Further, after the decorative sheet 200 is attached to the object to be decorated, the support 50 may be separated from the receiving layer 80 side.

As an example, the method for manufacturing a decorative sheet of the present disclosure includes a step of separating the support 50 from the receiving layer 80 side after the step of forming a thermal transfer image and before the step of transferring the aqueous adhesive layer 4. As another example, the method for manufacturing a decorative sheet of the present disclosure includes a step of separating the support 50 from the receiving layer side after the step of transferring the aqueous adhesive layer 4.

As for the separation auxiliary layer 70, when the receptive layer 80 side of the separation auxiliary layer is placed on top and the opposite side is placed on the bottom, (i) the upper surface of the separation auxiliary layer 70 (the surface on the receptive layer side) is prepared by physical means; (ii) Separation auxiliary layer 70 and constituent members located below the separation auxiliary layer can be separated (peelable) from the receiving layer 80 side with the separation auxiliary layer 70 as a separation interface; Composed of soluble components, the separation auxiliary layer is dissolved with water, and the separation auxiliary layer 70 and the constituent members located below the separation auxiliary layer 70 can be separated from the receiving layer 80 side; ( iii) An example is one in which the lower surface of the separation auxiliary layer 70 is used as a separation interface, and a component located below the separation interface can be separated from the receiving layer 80 side. The thickness of the separation auxiliary layer 70 is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 20 μm or less.

The separation auxiliary layer 70 of (i) contains a component having adhesive properties, and the adhesive force between the separation auxiliary layer 70 and the constituent members that are in contact with each other on the lower surface side of the separation auxiliary layer 70 and the separation auxiliary layer 70 is An example of this is a separation auxiliary layer 70 whose adhesive force is higher than the adhesive force with the constituent member (receiving layer 80 in the form shown in FIG. 3(b), durable layer 60 in the form shown in FIG. 3(c)) that contacts on the upper surface side. . As a method for adjusting the adhesive force, the upper surface of the constituent member (the support 50 in the form shown in FIG. 3) that contacts the lower side of the separation auxiliary layer 70 may be treated with corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, Examples include methods of performing surface treatments such as roughening treatment, chemical treatment, plasma treatment, low temperature plasma treatment, primer treatment, and grafting treatment. Note that if the adhesive force between the support 50 and the separation auxiliary layer 70 can be sufficiently increased without performing these surface treatments, the treatment is not necessary. Examples of the adhesive component include acrylic resin, vinyl resin, polyester, polyurethane, polyamide, epoxy resin, rubber resin, ionomer resin, and silicone resin.

Note that the adhesive force between the separation auxiliary layer 70 and the constituent members that are in contact with each other on the upper surface side of the separation auxiliary layer 70 (receptive layer 80 in the form shown in FIG. 3(b), durable layer 60 in the form shown in FIG. 3(c)) is If the height becomes too high and it is difficult to separate at the separation interface by using the upper surface of the separation auxiliary layer 70 as the separation interface, the constituent member in contact with the upper surface of the separation auxiliary layer 70 may be used as a release layer. In this form, the upper surface of the release layer may be used as a separation interface, or the lower surface of the release layer may be used as a separation interface. In the former case, the release layer constitutes the separation auxiliary layer 70. As the release layer, the release layer of the thermal transfer sheet 10 described later can be appropriately selected and used.

Further, instead of the separation auxiliary layer 70 having adhesive properties, a resin layer without adhesive properties may be used as the separation auxiliary layer 70. Examples of such resin layers include resin layers formed by extrusion methods such as extrusion coat lamination, sand lamination, and tandem lamination. Examples of the components of such a resin layer include polyesters such as polyethylene, polyethylene terephthalate, and polyethylene naphthalate, and polyolefins such as polypropylene, polybutene, polyisobutene, polybutadiene, polyisoprene, and ethylene-vinyl acetate copolymer.

Furthermore, the separation auxiliary layer 70 may contain various release agents to adjust the adhesive force between the separation auxiliary layer 70 and the constituent members in contact with it.

In addition, if it is desired to separate the support 50 after the step of forming a thermal transfer image or the step of forming an aqueous adhesive layer, it is possible to It is preferable to adjust the adhesion between the layers constituting the thermal transfer image-receiving sheet 100, particularly to prevent unintended separation at the separation interface for separating the support. Specifically, the adhesion force between each layer is determined by the peeling force when the receiving layer 80 and the dye layer 3 are brought into close contact with each other during the process of forming a thermal transfer image, and when the adhered dye layer is peeled off from the receiving layer, and the water-based adhesive. Layer 4 (heat-sealing layer when using the thermal transfer sheet of FIG. 5(b)) is brought into close contact with the receiving layer 80 side, and the aqueous adhesive layer 4 or heat-sealing layer that has been brought into close contact is placed on the base material 1 side of the thermal transfer sheet 10. It is desirable that the peeling force be higher than the peeling force used when peeling from.

The above-mentioned means for adjusting the adhesion force include means for surface-treating the support 50 of the thermal transfer image-receiving sheet described above, means for incorporating a release agent into the receptor layer 80, and means for adding a release agent to the dye layer 3 of the thermal transfer sheet 10. Examples include means for incorporating a molding agent, and means for providing a release layer between the base material 1 and the aqueous adhesive layer 4 of the thermal transfer sheet 10.

As the separation auxiliary layer 70 (ii), a conventionally known component (water-soluble resin) that can be dissolved in water can be appropriately selected and used. Examples of water-soluble components include polyethylene glycol, dextrin, polyvinylpyrrolidone, and polyvinyl alcohol.

Note that these components are common to the components exemplified in the water-based adhesive layer 4 described later, but, for example, appropriate dextrin in consideration of dextrin equivalent (DE value) and viscosity characteristic value (K value) are used. By selecting an appropriate polyvinylpyrrolidone and an appropriate polyvinyl alcohol in consideration of the degree of saponification and degree of polymerization, these components can be used as components soluble in water. Note that since polyvinylpyrrolidone and polyvinyl alcohol exhibit a certain degree of adhesiveness, when these components are used, it is desirable to use them together with dextrin and polyethylene glycol. In addition, other water-soluble components may be used.

The thickness of the separation auxiliary layer 70 containing water-soluble components is preferably 0.1 μm or more and 50 μm or less, more preferably 1 μm or more and 20 μm or less, and even more preferably 2 μm or more and 20 μm or less.

The separation auxiliary layer 70 of (iii) above has a structure in which the adhesive force between the separation auxiliary layer 70 and the constituent member in contact with the lower surface side of the separation auxiliary layer 70 is increased by the adhesive force between the separation auxiliary layer 70 and the constituent member in contact with the upper surface side of the separation auxiliary layer 70 ( Examples include a separation auxiliary layer 70 whose adhesive strength is lower than that of the receiving layer 80 in the form shown in FIG. 3(b) and the durable layer 60 in the form shown in FIG. 3(c).

In addition, when the support 50 has a laminated structure, instead of providing the separation auxiliary layer 70 between the support 50 and the receiving layer 80, or in addition to providing the separation auxiliary layer 70, it is possible to A separation auxiliary layer 70 may also be provided.

In the thermal transfer image-receiving sheet 100 having the separation auxiliary layer 70 described in (i) and (ii) above, when the upper surface of the separation auxiliary layer 70 is used as the separation interface, the layer that is in contact with the upper surface of the separation auxiliary layer 70 is , the decorative sheet 200 manufactured by the method for manufacturing a decorative sheet of the present disclosure is attached to an object to be decorated, and then, at the separation interface, the separation auxiliary layer 70 and the constituent members located below this are attached to the receiving layer. It is located at the outermost surface when separated from the 80 side. For example, when using the thermal transfer image-receiving sheet 100 shown in FIG. At this time, the receiving layer 80 on which the thermally transferred image is formed is located on the outermost surface of the decorative object after separation (see FIG. 4(a)).

When the separation auxiliary layer 70 as shown in (i) and (iii) above is used, the support 50 can be easily separated from the receptor layer 80 by physical means using the separation auxiliary layer. Therefore, by pasting the manufactured decorative sheet and the decorative object with water and separating them using the separation auxiliary layer 70 before or after this, a decorative article can be manufactured without taking the time required for manufacturing.

On the other hand, when using the water-soluble separation auxiliary layer 70 as shown in (ii) above, it is necessary to bring the separation auxiliary layer 70 into contact with water, and depending on the water permeability of the support 50, It takes a predetermined time to dissolve the separation auxiliary layer 70 with water. In particular, the support 50 as an example capable of forming a high-quality image includes a void layer having voids with low water permeability, a polyethylene terephthalate film, and the like. Therefore, when the purpose is to shorten the manufacturing time of decorative products using decorative sheets, it is preferable to use a material that can be separated by physical means as the separation auxiliary layer 70. On the other hand, when the separation auxiliary layer 70 is dissolved in water, the separation auxiliary layer 70 can also be dissolved using water when pasting the decorative sheet and the decoration object.

(Durable layer)
Therefore, when the purpose is to protect the image on the receptor layer 80 on which the thermally transferred image is formed, a durable layer 60 is provided between the separation auxiliary layer 70 and the receptor layer 80, as shown in FIG. 3(c). It is preferable to use a thermal transfer image-receiving sheet 100 that has been prepared. According to the thermal transfer image-receiving sheet 100 of this form, the decorative sheet 200 manufactured using the thermal transfer image-receiving sheet 100 of the form shown in FIG. When the support 50 is separated from the receiving layer 80 side, the durable layer 60 can be positioned on the outermost surface of the decoration object side after separation, and the durable layer 60 can impart durability to the thermal transfer image. (See FIG. 4(b)). Note that although FIGS. 4(a) and 4(b) show a form in which the separation auxiliary layer 70 and the support 50 are separated from the receiving layer 80 side, the separation auxiliary layer 70 is replaced by the separation auxiliary layer 70 described in (ii) above. 70, the separation auxiliary layer 70 is dissolved and removed, and the support 50 is separated from the receptor layer 80 side.

Components of the durable layer include ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, maleic acid-modified vinyl chloride-vinyl acetate copolymer, polyamide, polyester, polyethylene, ethylene-isobutyl acrylate copolymer, Butyral, polyvinyl acetate, and its copolymers, ionomer resins, acid-modified polyolefins, (meth)acrylic resins, acrylic ester resins, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic ester copolymers, Polymer, polymethyl methacrylate, cellulose resin, polyvinyl ether, polyurethane, polycarbonate, polypropylene, epoxy resin, phenolic resin, vinyl resin, maleic resin, alkyd resin, polyethylene oxide, urea resin, melamine resin, melamine-alkyd resin, silicone Resin, rubber resin, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene Examples include propylene-styrene block copolymer (SEPS), polystyrene, polyurethane, acrylic urethane, silicone-modified resins of these resins, cured products of actinic light-curable resins, and mixtures of these resins. The actinic ray-curable resin as used herein means a precursor or a composition before being irradiated with actinic rays. In addition, the term "actinic rays" as used herein refers to radiation that chemically acts on an actinic ray-curable resin to promote polymerization, and specifically includes visible rays, ultraviolet rays, X-rays, and electron beams. , α rays, β rays, γ rays, etc. The thickness of the durable layer 60 is preferably 0.5 μm or more and 10 μm or less.

The durable layer 60 can be formed by preparing a durable layer coating solution by dispersing or dissolving the components listed above in an appropriate solvent, and applying and drying this coating solution onto the separation auxiliary layer 70. . Alternatively, a polyethylene terephthalate film or a stretched or unstretched polypropylene film can be bonded to the support 50 or the separation auxiliary layer 70, and these films can be used as the durable layer 60.

Further, the durable layer 60 may be the separation auxiliary layer of (i) above.

<Thermal transfer sheet>
As shown in FIGS. 5(a) and 5(b), the thermal transfer sheet 10 as an example used in the decorative sheet manufacturing method of the present disclosure has a dye layer 3, an aqueous adhesive layer on the same side of the base material 1. 4 are provided in sequential order. Further, the aqueous adhesive layer 4 is provided so as to be peelable from the base material 1, and is transferred to the receptor layer 80 side of the thermal transfer image-receiving sheet 100 in the step of transferring the aqueous adhesive layer.

(Base material)
The base material 1 holds a dye layer 3, an aqueous adhesive layer 4, etc. provided on the base material 1. Materials for the base material 1 include polyester such as polyethylene terephthalate, polyarylate, polycarbonate, polyurethane, polyimide, polyetherimide, cellulose derivative, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polystyrene, acrylic, polyvinyl chloride, Polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetra Examples include various plastic films, sheets, cards, etc., such as fluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride.

There is no limitation on the thickness of the base material 1, and it is usually 2.5 μm or more and 100 μm or less. Furthermore, if necessary, one surface of the base material may be subjected to surface treatment. Examples of surface treatments include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, surface roughening treatment, chemical treatment, plasma treatment, low-temperature plasma treatment, primer treatment, grafting treatment, and the like.

(dye layer)
As shown in FIGS. 5(a) and 5(b), a dye layer 3 is provided on the base material 1 either directly or indirectly through another layer (for example, a dye primer layer to be described later). ing. The dye layer 3 contains a binder resin and a sublimable dye. There are no particular limitations on the binder resin, and cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, methyl cellulose, cellulose acetate, vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetoacetal, polyvinyl pyrrolidone, etc. ) Examples include acrylic resins such as acrylate and poly(meth)acrylamide, and resin components such as polyurethane, polyamide, and polyester.

Although there is no particular limitation on the content of the binder resin, the content of the binder resin with respect to the total mass of the dye layer 3 is preferably 20% by mass or more. By setting the binder resin content to 20% by mass or more with respect to the total mass of the dye layer, the sublimable dye can be sufficiently retained in the dye layer 3, and as a result, storage stability can be improved. There is no particular limitation on the upper limit of the content of the binder resin, and it may be set as appropriate depending on the content of the sublimable dye and any additives.

Although there are no particular limitations on the sublimable dye, it is preferable that it has sufficient coloring density and does not discolor or fade due to light, heat, temperature, etc. Dyes include diarylmethane dyes, triarylmethane dyes, thiazole dyes, merocyanine dyes, pyrazolone dyes, methine dyes, indoaniline dyes, acetophenone azomethine, pyrazoloazomethine, imidazolazomethine, imidazoazomethine, and pyridone azomethine. Azomethine dyes such as xanthene dyes, oxazine dyes, cyanostyrene dyes such as dicyanostyrene and tricyanostyrene, thiazine dyes, azine dyes, acridine dyes, benzene azo dyes, pyridone azo, thiophene azo, isothiazole Azo dyes such as azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, and disazo, spiropyran dyes, indorinospiropyran dyes, fluoran dyes, rhodamine lactam dyes, naphthoquinone dyes, anthraquinone dyes, Examples include quinophthalone dyes. Specifically, red dyes such as MSRedG (Mitsui Toatsu Chemical Co., Ltd.), Macrolex Red Violet R (Bayer AG), Ceres Red 7B (Bayer AG), Samaron Red F3BS (Mitsubishi Chemical Co., Ltd.), and Holon Brilliant Yellow dyes such as Yellow 6GL (Clariant), PTY-52 (Mitsubishi Chemical Co., Ltd.), Macrolex Yellow 6G (Bayer), Kayaset (registered trademark) Blue 714 (Nippon Kayaku Co., Ltd.), Holon Brilliant Blue SR (Clariant), MS Blue 100 (Mitsui Toatsu Chemical Co., Ltd.), C.I. I. Examples include blue dyes such as Solvent Blue 63.

The content of the sublimable dye is preferably 50% by mass or more and 350% by mass or less, more preferably 80% by mass or more and 300% by mass or less, based on the total mass of the binder resin. By setting the content of the sublimable dye to the above-mentioned preferable content, it is possible to further improve print density and storage stability.

Furthermore, in consideration of the releasability of the receptor layer 80 and the dye layer 3 in the process of forming a thermal transfer image, the dye layer 3 may contain a release agent. For example, when using the thermal transfer image-receiving sheet 100 provided with the separation auxiliary layer 70 described in (i) above as the thermal transfer image-receiving sheet 100, in order to suppress unintended peeling between the layers of the thermal transfer image-receiving sheet 100, dye The layer 3 may contain a release agent so that the peeling force between the dye layer 3 and the receiving layer 80 is smaller than the peeling force between these layers. The mass of the release agent relative to the total mass of the dye layer 3 is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 6% by mass or less.

As the mold release agent, silicone oil, phosphate ester, and silicone modified resin are preferred. Moreover, a mold release agent other than this may be used. Various modified silicone oils may be used as the silicone oil. Examples of the modified silicone oil include side chain type modified silicone oil, both end type modified silicone oil, single end type modified silicone oil, side chain both end type modified silicone oil, silicone graft acrylic resin, methylphenyl silicone oil, and the like.

Modified silicone oils are divided into reactive silicone oils and non-reactive silicone oils. Examples of reactive silicone oils include those modified with amino, epoxy, carboxyl, carbinol, methacrylic, mercapto, phenol, one-end reactivity, and different functional groups. Examples of the non-reactive silicone oil include those modified with polyether, methylstyryl, alkyl, higher fatty acid ester, hydrophilic special modification, higher alkoxy, higher fatty acid, and fluorine. For example, when using a thermal transfer image-receiving sheet 100 having a receiving layer 80 that does not contain a resin having hydroxyl groups, the dye layer 3 contains epoxy-modified silicone oil, and the receiving layer 80 contains a resin having hydroxyl groups. When using the thermal transfer image-receiving sheet 100 having the following, the dye layer 3 may contain polyether-modified silicone oil.

As the silicone modified resin, a method of block copolymerization of a thermoplastic resin and a polysiloxane group-containing vinyl monomer, a method of graft copolymerization of a thermoplastic resin and a polysiloxane group-containing vinyl monomer, or a method of graft copolymerization of a thermoplastic resin and a polysiloxane group-containing vinyl monomer, or a reactive silicone resin to a thermoplastic resin Examples include those prepared by a method of reacting. Examples of the thermoplastic resin constituting the silicone modified resin include polyvinyl acetal, acrylic resin, polyurethane, epoxy resin, polycarbonate, and polyimide. Among these, a copolymer of polyvinyl acetal and polysiloxane is preferred.

A reactive silicone resin is a compound that has a polysiloxane structure in its main chain and has a reactive functional group at one or both ends that reacts with a functional group of a thermoplastic resin. Examples of the reactive functional groups include amino groups, hydroxyl groups, epoxy groups, vinyl groups, and carboxyl groups.

There is no particular limitation on the method of forming the dye layer 3, and the dye layer may be formed by dispersing or dissolving additives such as the binder resin, sublimable dye, and release agent added as needed in an appropriate solvent. It can be formed by preparing a coating liquid for use in the coating, and applying and drying this coating liquid onto the base material 1 or a dye primer layer to be described later. The thickness of the dye layer 3 is preferably 0.2 μm or more and 2 μm or less.

Further, in order to improve the adhesion between the base material 1 and the dye layer 3, a dye primer layer may be provided between the base material 1 and the dye layer 3 (not shown). Examples of the components of the dye primer layer include resin components such as polyester, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic ester, polyvinyl acetate, polyurethane, styrene acrylate, polyacrylamide, polyamide, polyvinyl acetoacetal, and polyvinyl butyral. Further, the dye primer layer may contain various additives such as organic particles and inorganic particles together with these resin components.

There are no particular limitations on the method for forming the dye primer layer, and a coating solution for the dye primer layer is prepared by dispersing or dissolving the resin components exemplified above and additives added as necessary in an appropriate solvent. This coating liquid can be applied onto the base material 1 and dried. The thickness of the dye primer layer is preferably 0.02 μm or more and 1 μm or less.

In the illustrated embodiment, a yellow dye layer 3Y containing a yellow sublimable dye, a magenta dye layer 3M containing a magenta sublimable dye, and a cyan dye layer 3C containing a cyan sublimable dye are provided on the base material 1. Although the dye layer 3 is provided in a plane-sequential manner, a single dye layer 3 may be used, or two dye layers 3 may be provided in a plane-sequential manner.

Further, a structure may be adopted in which a heat-melting ink layer is provided in sequence with these dye layers 3. Examples of the components of the molten ink layer include dyes, organic colored pigments, fluorescent pigments, titanium oxide, zinc oxide, carbon black, iron oxide, iron yellow, ultramarine blue, hologram powder, aluminum powder, metallic pigments, pearl pigments, and the like. Further, a binder resin may be used together with these colorants.

(Aqueous adhesive layer)
As shown in FIGS. 5A and 5B, a dye layer 3 and an aqueous adhesive layer 4 are provided on the same surface of the base material 1 in plane order. The water-based adhesive layer 4 is provided so as to be peelable from the base material 1 side, and is a layer that is transferred to the receptor layer 80 side in the process of transferring the water-based adhesive layer, and is manufactured by the decorative sheet manufacturing method of the present disclosure. It is located on the outermost surface of the decorative sheet 200. The aqueous adhesive layer 4 is a layer whose adhesiveness (sometimes referred to as adhesion or adhesion) increases due to water absorption, or which exhibits adhesiveness due to water absorption. Therefore, the components of the aqueous adhesive layer 4 are not particularly limited as long as they have this property. Further, as long as it exhibits the above-mentioned properties, it may be partially dissolved by water absorption.

Ingredients that can exhibit the above properties include polyacrylamide, polyvinyl methyl ether, acrylic acid copolymers, starch, dextrin, glue, animal proteins such as gelatin, celluloses such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose, polyvinylpyrrolidone, polyvinyl Examples include alcohol, latex emulsions of natural rubber and synthetic rubber, copolymers of acrylic esters, vinyl acetate emulsions, and sorbitol. Among these, starch, dextrin, polyvinylpyrrolidone, and polyvinyl alcohol are preferred. Particularly preferred are pregelatinized starch, which easily swells in cold water and exhibits stickiness, and dextrin, polyvinylpyrrolidone, and polyvinyl alcohol, which are sparingly soluble or insoluble in water. The aqueous adhesive layer 4 may contain one type of component capable of exhibiting the above properties, or may contain two or more types capable of expressing the above properties.

There is no limitation on the content of the component capable of exhibiting the above properties, and as an example, it is 50% by mass or more, preferably 80% by mass or more, based on the total mass of the aqueous adhesive layer 4.

Further, the aqueous adhesive layer 4 may contain other components in addition to the components capable of exhibiting the above properties. For example, it may contain a component that adjusts the strength of the aqueous adhesive layer 4 in addition to a component that can exhibit the above-mentioned properties. Examples of such components include polyester, polyurethane, acrylic resin, vinyl chloride-vinyl acetate copolymer, and the like.

Further, as shown in FIG. 5(a), when the thermal transfer sheet 10 is such that when the aqueous adhesive layer 4 is transferred onto the receptive layer 80, the receptive layer 80 and the aqueous adhesive layer 4 are in direct contact with each other. It is preferable that the aqueous adhesive layer 4 also contains a component having a hydroxyl group, similar to the receptor layer 80 described above. By containing a component having a hydroxyl group in the aqueous adhesive layer 4, the adhesion between the receptor layer 80 and the aqueous adhesive layer 4 can be improved. The component having a hydroxyl group may be selected from among the components capable of exhibiting the above properties, or other components having a hydroxyl group may be used.

There is no limitation on the thickness of the aqueous adhesive layer 4, but it is preferably 1 μm or more and 50 μm or less, more preferably 2 μm or more and 35 μm or less.

There is no limitation on the method of forming the aqueous adhesive layer 4, and the above-mentioned components whose adhesiveness increases or develops adhesiveness due to water absorption, other resin components added as necessary, and additives are mixed in a suitable solvent. Prepare an aqueous adhesive layer coating solution dispersed or dissolved in , can be formed by coating and drying.

(Release layer)
As shown in FIG. 5(b), a release layer 2 may be provided between the base material 1 and the aqueous adhesive layer 4. According to this embodiment, when transferring the aqueous adhesive layer 4, the aqueous adhesive layer 4 can be easily peeled off from the base material 1, and when transferring the aqueous adhesive layer 4 onto the receiving layer 80 on which a thermal transfer image has been formed. , it is possible to suppress unintended separation (peeling) between the layers constituting the thermal transfer image-receiving sheet 100. This form is particularly suitable when the thermal transfer image-receiving sheet 100 used in the decorative sheet manufacturing method of the present disclosure is the thermal transfer image-receiving sheet 100 having the separation auxiliary layer 70. Note that when the water-based adhesive layer 4 can be easily transferred without providing the release layer 2, or during the process of transferring the water-based adhesive layer without providing the release layer 2, there may be a difference between each layer constituting the thermal transfer image-receiving sheet 100. If unintended separation (peeling) does not occur, it is not particularly necessary to provide the release layer 2.

Components of the release layer 2 include waxes, silicone wax, silicone resin, various silicone-modified resins such as silicone-modified acrylic resin, fluororesin, fluorine-modified resin, polyvinyl alcohol, acrylic resin, acrylic-styrene copolymer, and heat. Examples include curable epoxy-amino copolymers, thermosetting alkyd-amino copolymers (thermosetting amino alkyd resins), melamine resins, cellulose resins, urea resins, and polyolefins. Furthermore, the release layer 2 may contain various fillers and the like.

The thickness of the release layer 2 is preferably 0.1 μm or more and 10 μm or less.

(heat seal layer)
As shown in FIG. 5(b), a heat seal layer 5 may be provided on the aqueous adhesive layer 4. That is, a transfer layer is provided on the base material 1, and this transfer layer may have a laminated structure in which the aqueous adhesive layer 4 and the heat seal layer 5 are laminated in this order from the base material 1 side. Note that the aqueous adhesive layer 4 is located closest to the base material 1 among the layers constituting the transfer layer. The transfer layer including the aqueous adhesive layer 4 may also include layers other than this. According to this type of thermal transfer sheet, by transferring the transfer layer, the receiving layer 80 and the aqueous adhesive layer 4 can be firmly adhered to each other by the heat seal layer included in the transfer layer. Components of the heat seal layer 5 include polyester, vinyl chloride-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane, polyolefin such as α-olefin-maleic anhydride, polyvinyl acetate, urea resin, melamine resin, and phenol. Examples include resins and cyanoacrylates. Among these, polyester, vinyl chloride-vinyl acetate copolymer, acrylic resin, and epoxy resin are preferred. Moreover, those resins cured with a curing agent can also be used. Examples of the curing agent include isocyanate compounds, aliphatic amines, cycloaliphatic amines, aromatic amines, and acid anhydrides.

Further, when using the thermal transfer sheet 10 of this form, the receiving layer 80 and the heat seal layer 5 come into contact with each other in the step of transferring the aqueous adhesive layer. Therefore, in order to further improve the adhesion between the receptor layer 80 and the heat seal layer 5, it is preferable that both the receptor layer 80 and the heat seal layer 5 contain a component having a hydroxyl group. For example, it is preferable that both the receptor layer 80 and the heat seal layer 5 contain a vinyl chloride-vinyl acetate copolymer having a hydroxyl group.

Furthermore, by forming both the heat seal layer 5 and the aqueous adhesive layer 4 to contain a component having a hydroxyl group, the adhesion between the heat seal layer 5 and the aqueous adhesive layer 4 can be improved.

Further, the heat seal layer 5 may contain a coloring agent. By using the heat-sealing layer 5 containing a colorant, the base of the decorative object can be hidden when the decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure is attached to the decorative object.

Examples of colorants include dyes, organic colored pigments, fluorescent pigments, calcium carbonate, titanium oxide, zinc oxide, silica, carbon black, iron oxide, iron yellow, ultramarine blue, hologram powder, aluminum powder, metallic pigments, pearl pigments, etc. can. Among these, white pigments are preferred.

The thickness of the heat seal layer 5 is generally 2 μm or more and 10 μm or less.

There is no particular limitation on the method for forming the heat seal layer 5, and a coating liquid for the heat seal layer is prepared by dispersing or dissolving the components exemplified above and additives added as necessary in an appropriate solvent. The coating liquid can be applied and dried on the base material 1 or on a layer arbitrarily provided on the base material 1 (for example, a release layer).

Moreover, instead of containing a coloring agent in the heat-sealing layer 5, or in addition to this, the water-based adhesive layer 4 may contain a coloring agent. Further, a concealing layer containing a colorant may be provided between the aqueous adhesive layer 4 and the heat seal layer 5.

(back layer)
Further, a back layer (not shown) may be provided on the other surface of the base material 1. Components of the back layer include polyester, polyacrylic acid ester, polyvinyl acetate, styrene acrylate resin, polyolefin such as polyurethane, polyethylene, and polypropylene, polystyrene, polyvinyl chloride, polyether, polyamide, polyimide, polyamideimide, polycarbonate, and polyester. Examples include polyvinyl acetals such as acrylamide, polyvinyl chloride, polyvinyl butyral, and polyvinyl acetoacetal, and silicone modified products thereof.

In addition, the back layer may contain wax, higher fatty acid amide, phosphoric acid ester compound, metal soap, silicone oil, mold release agent such as surfactant, organic powder such as fluororesin, inorganic material such as silica, clay, talc, calcium carbonate, etc. It may contain various additives such as particles. 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.

In the above, the thermal transfer sheet 10 used in the method for manufacturing a decorative sheet of the present disclosure is a thermal transfer sheet 10 in which the dye layer 3 and the water-based adhesive layer 4 are sequentially provided on the same side of the base material 1. The formation of a thermal transfer image and the transfer of an aqueous adhesive layer are carried out using this method. A second thermal transfer sheet 10 is provided with an aqueous adhesive layer 4, a thermal transfer image is formed using the first thermal transfer sheet 10, and the aqueous adhesive layer 4 is transferred using the second thermal transfer sheet 10. Good too. In addition, according to the thermal transfer sheet 10 in which the dye layer 3 and the water-based adhesive layer 4 are sequentially provided on the same side of the base material 1, just by using this thermal transfer sheet, the final product of the decorative sheet can be created. This is preferable because it can be manufactured in batches.

In the above, an example is described in which a thermal transfer sheet having an aqueous adhesive layer 4 is used to form an aqueous adhesive layer 4 (a single layer including the aqueous adhesive layer 4 or a layered structure transfer layer) on an image formed object by transfer. Although the explanation has focused on the process of forming the water-based adhesive layer as another example, the water-based adhesive layer 4 in the form of a film or sheet is formed using an adhesive layer (which may be an adhesive film or an adhesive sheet). to form an image by pasting it onto the image formed object.

The aqueous adhesive layer 4 in the form of a film or sheet may be one that increases its adhesiveness by absorbing water or exhibits adhesiveness by absorbing water. The thickness of the film or sheet-like aqueous adhesive layer 4 is preferably 2 μm or more and 150 μm or less, more preferably 2 μm or more and 50 μm or less.

A method for forming such a film or sheet-like aqueous adhesive layer 4 on an image-formed object is to form an adhesive layer on the image-formed object, or on a film or sheet-like aqueous adhesive layer 4. Examples include a method of bonding the image formed product and the aqueous adhesive layer 4 via this adhesive layer. The adhesive layer may be formed by dissolving or dispersing a component having adhesive properties in a suitable solvent and applying a coating liquid, followed by drying. Alternatively, the adhesive layer may be formed by transfer using a transfer sheet capable of transferring the adhesive layer. Alternatively, a film or a sheet-like adhesive layer may be used, and this may be bonded to the image-formed product or the aqueous adhesive layer 4 to form the adhesive layer.

Furthermore, as a film or sheet-like adhesive layer, an adhesive layer with a masking member may be used on one or both surfaces thereof. The masking member may be any material as long as it can be peeled off from the adhesive layer. As such a masking member, those conventionally known in the field such as a release film, a separate paper, a separate film, a release film, a release paper, etc. can be appropriately selected and used. Alternatively, it may be a resin layer. The masking member is composed of a component having mold releasability, and examples of the component having mold releasability include silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester, and wax.

FIGS. 6(a) to 6(c) are schematic cross-sectional views showing an example of a decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure. The decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure is not limited to the form shown in FIG. 6, and may have a configuration combining these. Further, another layer may be provided between each layer.

(Trimming process)
The decorative sheet manufacturing method of the present disclosure includes a thermal transfer image-receiving sheet 100, an image-formed product in which an image is formed on the receptor layer 80 of the thermal-transfer image-receiving sheet, or a decorative sheet in which an aqueous adhesive layer 4 is provided on the image-formed product. A trimming step of cutting in the thickness direction may be included to obtain an arbitrary shape. In other words, it may include a trimming step to give the final manufactured decorative sheet an arbitrary shape.

For example, the thermal transfer image-receiving sheet 100 used in the decorative sheet manufacturing method of the present disclosure may include a film or a sheet-like durable layer 60, or the aqueous adhesive layer 4 formed on the image formed object may be a film or a sheet. If the decorative sheet has a shape, trimming may be performed between appropriate steps or after the step, so that the planar shape of the manufactured decorative sheet can be made into a desired shape. There is no limitation on the portion to be trimmed, and examples include the outer edge of the thermal transfer image formed on the receptor layer 80 of the thermal transfer image-receiving sheet 100 or the outer edge of the area including the thermal transfer image. Examples of the trimming method include cutting using a cutter or the like.

(Decoration object)
The decorative object to be bonded to the decorative sheet 200 manufactured by the decorative sheet manufacturing method of the present disclosure is not limited in shape, size, material, etc., and may be of any type. For example, it may be paper, a resin plate, a metal plate, a glass plate, a ceramic plate, etc. The decorative sheet 200 manufactured by the method for manufacturing a decorative sheet of the present disclosure may be used as a tattoo sticker, and the decoration object may be a human body. Further, the entire or part of the decorative object may have a curvature, an uneven structure, or the like.

<<Method for manufacturing decorative items>>
Next, a method for manufacturing an ornament according to an embodiment of the present disclosure will be described using the first to third embodiments as examples.

(Method for manufacturing ornaments according to the first embodiment)
The method for manufacturing a decorative article according to the first embodiment includes a step of integrating a decorative object and a decorative sheet. In the method for manufacturing a decorative article of the present disclosure, the decorative sheet manufactured by the method for manufacturing a decorative sheet of the present disclosure is used as the decorative sheet, and the decorative object and the decorative sheet are integrated using water. let

(Method for manufacturing ornaments according to second embodiment)
The method for manufacturing a decorative article according to the second embodiment includes a step of integrating a decorative object and a decorative sheet, and as a decorative sheet, the adhesiveness increases due to water absorption on an image formed object on which a thermally transferred image is formed. Or use one provided with an aqueous adhesive layer that develops adhesiveness by absorbing water.

As such a decorative sheet, the structure of the decorative sheet 200 manufactured by the above-described method for manufacturing a decorative sheet of the present disclosure can be appropriately selected and used. Note that the decorative sheet used in the method for manufacturing a decorative article according to the second embodiment is not limited to that manufactured by the method for manufacturing a decorative sheet according to the present disclosure.

(Method for manufacturing ornaments according to third embodiment)
Further, the method for manufacturing a decorative article according to the third embodiment includes a step of forming an aqueous adhesive layer on a decorative object, the adhesiveness of which increases due to absorption of water, or which exhibits adhesiveness due to absorption of water; Before or after this process, a thermal transfer image-receiving sheet with a receptor layer provided on a support and a thermal transfer sheet with a dye layer containing a sublimable dye on a base material are combined, and the dye layer contains a sublimable dye. A step of preparing an image-formed object in which a thermally transferred image is formed on the receiving layer by transferring a sublimable dye to a receiving layer; and a step of integrating.

The decorative article manufacturing methods of the first and second embodiments use a decorative sheet in which an aqueous adhesive layer is provided on the image formed object, whereas the decorative article manufacturing method of the third embodiment differs in that, instead of forming an aqueous adhesive layer on the image-formed object, a water-based adhesive layer is formed on the decorative object and this and the image-formed object are integrated using water, Other than this, they match.

The formation of the image formed object used in the method for manufacturing a decorative article according to the third embodiment is the same as the step of forming an image in the method for manufacturing a decorative sheet according to the present disclosure. The aqueous adhesive layer can be formed on the decorative object by appropriately selecting the method described in the step of forming the aqueous adhesive layer of the decorative sheet manufacturing method of the present disclosure.

According to the method for manufacturing a decorative article according to each embodiment of the present disclosure, a decorative article having a high design quality can be manufactured by a simple method.

＜＜Decorative sheet＞＞
Next, a decorative sheet according to an embodiment of the present disclosure (hereinafter referred to as a decorative sheet of the present disclosure) will be described.

The decorative sheet 200 of the present disclosure includes an image-formed product having an image and an aqueous adhesive layer 4 provided on the image-formed product. In the decorative sheet 200 of the present disclosure, the aqueous adhesive layer 4 is an aqueous adhesive layer 4 whose adhesiveness increases or exhibits adhesiveness due to water absorption.

According to the decorative sheet 200 of the present disclosure, similar to the decorative sheet 200 manufactured by the above-described method of manufacturing a decorative sheet of the present disclosure, the decorative sheet 200 and the decorative object can be attached by simply making the aqueous adhesive layer 4 absorb water. You can manufacture matching ornaments. In other words, the decorative sheet 200 of the present disclosure can be used to easily decorate the decorative object 300.

As the aqueous adhesive layer 4, the aqueous adhesive layer 4 explained in the method for producing a decorative sheet of the present disclosure can be used as is, and detailed description thereof will be omitted here. Further, other layers, such as a protective layer, may be provided on the aqueous adhesive layer 4. Further, another layer, such as the heat seal layer described in the method for producing a decorative sheet of the present disclosure, may be provided between the image formed product and the aqueous adhesive layer 4.

(Image formed product)
The imaged product has an image. There is no limitation on the type of image, and examples include images formed by a sublimation type thermal transfer method, a melting type thermal transfer method, an inkjet printing method, a toner printing method (laser printing method), and the like. Furthermore, the image may be formed by a method other than this. An example of an imaged product has a laminated structure including a support and an image layer on which an image is formed. The image-formed product may have a single-layer structure consisting only of an image layer having an image. Moreover, the support body may have a laminated structure consisting of a plurality of constituent members. In a preferable decorative sheet of the present disclosure, the image of the image formed product is an image formed by a sublimation type thermal transfer method. According to the decorative sheet of this form, the image on the decorative sheet can be of high quality.

The image-formed product as an example has a structure in which a thermal transfer image is formed on the receiving layer of the thermal transfer image-receiving sheet 100 described in the method for manufacturing a decorative sheet of the present disclosure.

Next, the present invention will be explained in more detail with reference to Examples. Hereinafter, unless otherwise specified, parts are based on mass, and are the mass before being converted to solid content (the amount charged).

(Creation of thermal transfer sheet 1)
A polyethylene terephthalate film with a thickness of 4.5 μm is used as the base material 1, and a back layer coating liquid having the following composition is applied to one side of the base material 1 to a thickness of 1 μm and dried to form a back layer. Formed. Next, a part of the surface opposite to the surface on which the back layer was formed was subjected to corona treatment, and a primer layer coating liquid having the following composition was applied to the corona-treated portion to a thickness of 0.1 μm. - Dry to form a primer layer. Next, on the primer layer, coating liquid 1 for yellow dye layer, coating liquid 1 for magenta dye layer, and coating liquid 1 for cyan dye layer having the following compositions were applied and dried to a thickness of 0.5 μm. Then, a yellow dye layer, a magenta dye layer, and a cyan dye layer were sequentially formed. In addition, on the part of the base material 1 opposite to the side on which the back layer was formed, where no corona treatment has been performed, aqueous adhesive layer coating liquid 1 having the following composition was applied and dried to a thickness of 4 μm. to form a water-based adhesive layer, and on this water-based adhesive layer, apply Coating Liquid 1 for heat-sealing layer having the following composition to a thickness of 1 μm and dry to form a heat-sealing layer. was formed to obtain a thermal transfer sheet 1.

<Coating liquid for back layer>
・Polyvinyl butyral 3.6 parts (S-LEC (registered trademark) BX-1 Sekisui Chemical Co., Ltd.)
・Polyisocyanate 8.4 parts (Burnock (registered trademark) D750 DIC Corporation)
・Phosphate ester surfactant 2.8 parts (Prysurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・Talc 0.6 parts (Micro Ace (registered trademark) P-3 Nippon Talc Industries Co., Ltd.)
・Toluene 42.3 parts ・Methyl ethyl ketone 42.3 parts

<Coating liquid for primer layer>
・Alumina sol 5 parts (Alumina sol 200 Nissan Chemical Industries, Ltd.)
・Water 47.5 parts ・Isopropyl alcohol 47.5 parts

<Yellow dye layer coating liquid 1>
・Solvent Yellow 93 2.5 parts ・Disperse Yellow 201 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Toluene 46 parts ・Methyl ethyl ketone 46 parts

<Coating liquid 1 for magenta dye layer>
・Disperse Violet 26 2.5 parts ・Disperse Violet 60 2 parts ・Disperse Red 343 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Toluene 45 parts ・Methyl ethyl ketone 45 parts

<Coating liquid 1 for cyan dye layer>
・Solvent Blue 63 3.5 parts ・Disperse Blue 354 1.5 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Toluene 45.75 parts ・Methyl ethyl ketone 45.75 parts

<Coating liquid 1 for water-based adhesive layer>
・Polyvinylpyrrolidone 5 parts (K-90 ISP Japan Co., Ltd.)
・Water 45 parts ・Isopropyl alcohol 50 parts

<Coating liquid 1 for heat seal layer>
- Vinyl chloride-vinyl acetate copolymer (hydroxyl group-containing) 20 parts (Solvine (registered trademark) AL Nissin Chemical Industry Co., Ltd.)
・Toluene 26.7 parts ・Methyl ethyl ketone 53.3 parts

(Creation of thermal transfer sheet 2)
Coating liquid 1 for yellow dye layer, coating liquid 1 for magenta dye layer, and coating liquid 1 for cyan dye layer were respectively converted into coating liquid 2 for yellow dye layer and coating liquid 2 for magenta dye layer with the following compositions. Thermal transfer sheet 2 was prepared in the same manner as thermal transfer sheet 1 except that the coating liquid 2 for cyan dye layer was changed to form a yellow dye layer, a magenta dye layer, and a cyan dye layer each having a thickness of 0.5 μm. I got it.

<Yellow dye layer coating liquid 2>
・Solvent Yellow 93 2.5 parts ・Disperse Yellow 201 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Silicone oil 0.08 part (KF101 Shin-Etsu Chemical Co., Ltd.)
・Toluene 45.96 parts ・Methyl ethyl ketone 45.96 parts

<Coating liquid 2 for magenta dye layer>
・Disperse Violet 26 2.5 parts ・Disperse Violet 60 2 parts ・Disperse Red 343 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Silicone oil 0.1 part (KF101 Shin-Etsu Chemical Co., Ltd.)
・Toluene 44.95 parts ・Methyl ethyl ketone 44.95 parts

<Coating liquid 2 for cyan dye layer>
・Solvent Blue 63 3.5 parts ・Disperse Blue 354 1.5 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Silicone oil 0.09 part (KF101 Shin-Etsu Chemical Co., Ltd.)
・Toluene 45.71 parts ・Methyl ethyl ketone 45.71 parts

(Creation of thermal transfer sheet 3)
Coating liquid 1 for aqueous adhesive layer was changed to coating liquid for peeling auxiliary layer having the following composition to form a peeling auxiliary layer with a thickness of 1 μm, and coating liquid 1 for heat sealing layer was changed to coating liquid for heat sealing layer having the following composition. Thermal transfer sheet 3 was obtained in the same manner as thermal transfer sheet 1 except that coating liquid 2 was used and a heat seal layer having a thickness of 1 μm was formed on the release auxiliary layer. The peeling auxiliary layer is a layer that does not have adhesiveness due to water absorption, and is a layer that is peeled off at the interface with the base material.

<Coating liquid A for transfer layer>
・Acrylic resin 19.5 parts (Dyanal (registered trademark) BR-83 Mitsubishi Chemical Corporation)
・Polyester 0.5 part (Byron (registered trademark) 200 Toyobo Co., Ltd.)
・Toluene 40 parts ・Methyl ethyl ketone 40 parts

<Coating liquid 2 for heat seal layer>
・Polyester (containing hydroxyl group) 20 parts (Vylon (registered trademark) 200 Toyobo Co., Ltd.)
・Toluene 40 parts ・Methyl ethyl ketone 40 parts

(Creation of thermal transfer sheet 4)
As the base material 2, a polyethylene terephthalate film with a thickness of 4.5 μm that has been subjected to an easy-adhesion treatment on one side is used, and on the side of the base material 2 that has not been subjected to an easy-adhesion treatment, a back layer having the above composition is used. A back layer was formed by applying a coating solution to a thickness of 1 μm and drying. Next, a yellow dye layer coating liquid 3, a magenta dye layer coating liquid 3, and a cyan dye layer coating liquid 3 having the following compositions were applied to a part of the surface where the easy-adhesion layer was formed to a thickness of 0.5 μm. A yellow dye layer, a magenta dye layer, and a cyan dye layer were sequentially formed by coating and drying the layers as follows. Next, on another part of the surface of the base material 2 that has been subjected to the adhesion treatment, a release layer coating liquid having the following composition is applied to a thickness of 1 μm and dried to form a release layer. Aqueous adhesive layer coating liquid 2 having the following composition was applied onto this release layer to a thickness of 4 μm and dried to form an aqueous adhesive layer. Next, a heat-sealing layer coating liquid 3 having the following composition was applied onto the aqueous adhesive layer to a thickness of 3.5 μm and dried to form a heat-sealing layer, thereby obtaining a thermal transfer sheet 4.

<Yellow dye layer coating liquid 3>
・Solvent Yellow 93 2.5 parts ・Disperse Yellow 201 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Phosphate ester surfactant 0.11 parts (Prysurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・Toluene 45.95 parts ・Methyl ethyl ketone 45.95 parts

<Coating liquid 3 for magenta dye layer>
・Disperse Violet 26 2.5 parts ・Disperse Violet 60 2 parts ・Disperse Red 343 2 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Phosphate ester surfactant 0.11 parts (Prysurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・Toluene 44.95 parts ・Methyl ethyl ketone 44.95 parts

<Coating liquid 3 for cyan dye layer>
・Solvent Blue 63 3.5 parts ・Disperse Blue 354 1.5 parts ・Polyvinyl acetal 3.5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Phosphate ester surfactant 0.11 parts (Prysurf (registered trademark) A208N Daiichi Kogyo Seiyaku Co., Ltd.)
・Toluene 45.7 parts ・Methyl ethyl ketone 45.7 parts

<Coating liquid for release layer>
・Silicone modified acrylic resin 9.5 parts (Celltop (registered trademark) 226 Daicel Corporation)
・Polyether modified silicone 0.5 part (KF-6011 Shin-Etsu Chemical Co., Ltd.)
・Toluene 45 parts ・Methyl ethyl ketone 45 parts

<Coating liquid 2 for water-based adhesive layer>
・Polyvinyl alcohol 5 parts (PVA-217 Kuraray Co., Ltd.)
・Water 45 parts ・Isopropyl alcohol 50 parts

<Coating liquid 3 for heat seal layer>
・Vinyl chloride-vinyl acetate copolymer (containing hydroxyl group) 10 parts (Solvine (registered trademark) AL Nissin Chemical Industry Co., Ltd.)
・Polyester 10 parts (Byron (registered trademark) 200 Toyobo Co., Ltd.)
・Titanium oxide 24 parts (TCA-888 Tochem Products Co., Ltd.)
・Toluene 28 parts ・Methyl ethyl ketone 28 parts

(Creation of thermal transfer sheet 5)
Thermal transfer sheet 5 was obtained in the same manner as thermal transfer sheet 4, except that water-based adhesive layer coating liquid 2 was changed to water-based adhesive layer coating liquid 3 having the following composition to form an aqueous adhesive layer with a thickness of 4 μm. Ta.

<Coating liquid 3 for water-based adhesive layer>
・Polyvinyl alcohol 4 parts (PVA-217 Kuraray Co., Ltd.)
・1 part dextrin (HiCoaster (registered trademark) PC-11 Sanwa Starch Industries Co., Ltd.)
・Water 45 parts ・Isopropyl alcohol 50 parts

(Creation of thermal transfer sheet 6)
Thermal transfer sheet 6 was obtained by replacing the H panel portion of HID FARGO (registered trademark) HDP5000 printer media (YMCKH 500IMAGE) with the following panel.

(Creating a panel)
As the base material 2, a polyethylene terephthalate film with a thickness of 4.5 μm that has been subjected to an easy-adhesion treatment on one side is used, and a back layer coating having the above composition is applied to the side that has not been subjected to an easy-adhesion treatment. A back layer was formed by applying and drying a working solution to a thickness of 1 μm. Next, a release layer coating solution having the above composition is applied to the surface on which the easy-adhesion layer is formed, and dried to a thickness of 1 μm to form a release layer. Coating liquid 3 for adhesive layer was applied and dried to a thickness of 4 μm to form an aqueous adhesive layer. Next, a heat seal layer was formed by applying and drying a heat seal layer coating liquid 4 having the following composition on the aqueous adhesive layer to a thickness of 3.5 μm, thereby forming a panel to replace the H panel portion. .

<Coating liquid 4 for heat seal layer>
・20 parts of vinyl chloride-vinyl acetate copolymer (Solvine (registered trademark) C Nissin Chemical Industry Co., Ltd.)
・Toluene 26.7 parts ・Methyl ethyl ketone 53.3 parts

(Creation of thermal transfer image receiving sheet 1)
A polyethylene terephthalate film (CRISPR (registered trademark) K1212 Toyobo Co., Ltd.) with a thickness of 125 μm was used as the support (1), and a coating liquid for a separation auxiliary layer having the following composition was applied to one side of the support (1). 1 was coated and dried to a thickness of 5 μm to form a separation auxiliary layer, and on this separation auxiliary layer, a polyethylene terephthalate film (25 μm thick) with an easy-adhesion treatment on one side was placed as a durable layer. E5101 (Toyobo Co., Ltd.) was bonded so that the surface that had not been subjected to the easy-adhesion treatment was in contact with the separation auxiliary layer. Next, a receptive layer was formed by applying and drying a receptive layer coating liquid 1 having the following composition to a thickness of 4 μm on the adhesive-treated surface of the polyethylene terephthalate film as a durable layer, followed by thermal transfer. Image receiving sheet 1 was obtained.

<Coating liquid 1 for separation auxiliary layer>
・Silicone adhesive 20 parts (X40-3229 Shin-Etsu Chemical Co., Ltd.)
・Catalyst 0.1 part (CAT-PL-50T Shin-Etsu Chemical Co., Ltd.)
・Toluene 39.95 parts ・Methyl ethyl ketone 39.95 parts

<Coating liquid 1 for receptor layer>
・25 parts of vinyl chloride-vinyl acetate copolymer (Solvine (registered trademark) CNL Nissin Chemical Industry Co., Ltd.)
・1 part silicone oil (X22-3000T Shin-Etsu Chemical Co., Ltd.)
・Silicone oil 0.5 part (X24-510T Shin-Etsu Chemical Co., Ltd.)
・Methyl ethyl ketone 55 parts ・Toluene 18.5 parts

(Creation of thermal transfer image receiving sheet 2)
A polyethylene terephthalate film (E5101, Toyobo Co., Ltd.) with a thickness of 25 μm, which had been treated with easy adhesion on one side, was used as the durable layer. Coating liquid 2 for receptor layer having the following composition was applied to the side which had been treated with easy adhesion. Apply and dry to a thickness of 4 μm to form a receptive layer, and then apply coating liquid 1 for release layer having the following composition to a thickness of 0.25 μm on the surface that has not been treated for easy adhesion. - A release layer was formed by drying, and on this release layer, coating liquid 2 for separation auxiliary layer having the following composition was applied to a thickness of 10 μm and dried to form a separation auxiliary layer. Next, the separation auxiliary layer and a polyethylene terephthalate film (CRISPR (registered trademark) K1212 Toyobo Co., Ltd.) having a thickness of 125 μm as a support (1) were bonded together to obtain a thermal transfer image-receiving sheet 2.

<Receptive layer coating liquid 2>
- Vinyl chloride-vinyl acetate copolymer (hydroxyl group-containing) 20 parts (Solvine (registered trademark) A Nissin Chemical Industry Co., Ltd.)
・Silicone oil 0.5 part (KF-615 Shin-Etsu Chemical Co., Ltd.)
・Silicone oil 1.5 parts (X62-1421B Shin-Etsu Chemical Co., Ltd.)
・Xylene diisocyanate 6.5 parts (Takenate (registered trademark) A-14 Mitsui Chemicals, Inc.)
・Methyl ethyl ketone 53.63 parts ・Toluene 17.88 parts

<Coating liquid 1 for release layer>
・Addition polymerization agent silicone 30 parts (KS-847 Shin-Etsu Chemical Co., Ltd.)
・Catalyst 0.09 part (CAT-PL-50T Shin-Etsu Chemical Co., Ltd.)
・Ethyl acetate 69.91 parts

<Coating liquid 2 for separation auxiliary layer>
・Acrylic copolymer 30 parts (SK Dyne 1251 Soken Chemical Co., Ltd.)
・Curing agent 0.66 parts (Curing agent L-45 Soken Chemical Co., Ltd.)
・Curing agent 0.2 parts (Curing agent E-AX Soken Chemical Co., Ltd.)
・Ethyl acetate 69.14 parts

(Creation of thermal transfer image receiving sheet 3)
Thermal transfer image-receiving sheet 3 was prepared in the same manner as thermal transfer image-receiving sheet 2, except that release layer coating liquid 1 was changed to release layer coating 2 having the following composition to form a release layer with a thickness of 0.5 μm. Obtained.

<Coating liquid 2 for release layer>
・Polyvinyl acetal 5 parts (S-LEC (registered trademark) KS-5 Sekisui Chemical Co., Ltd.)
・Methyl ethyl ketone 47.5 parts ・Toluene 47.5 parts

(Creation of thermal transfer image receiving sheet 4)
White base paper (uncoated paper, thickness 150 μm (Mitsubishi Paper Mills, Ltd.) was used as the paper base material, and porous polypropylene film (thickness The paper base material and the porous polypropylene film ^were pasted together using melt-extruded polyethylene having a thickness of 15 μm while passing between a pair of rollers to form a support ( 2) was formed. On the porous polypropylene film of the support 2, a separation auxiliary layer coating solution 3 having the following composition was applied and dried to a thickness of 5 μm to form a separation auxiliary layer. On the auxiliary layer, a durable layer coating liquid having the following composition was applied and dried to a thickness of 2 μm to form a durable layer.Next, on the durable layer, a receptor layer coating liquid 2 having the above composition was applied. A receptor layer was formed by coating and drying to a thickness of 4 μm, and a thermal transfer image-receiving sheet 4 was obtained.

<Coating liquid 3 for separation auxiliary layer>
・Polyvinyl alcohol 2 parts (PVA-203 Kuraray Co., Ltd.)
・Dextrin 8 parts (HiCoaster (registered trademark) PC-11 Sanwa Starch Industries Co., Ltd.)
・Wednesday 90 parts

<Coating liquid for durable layer>
・Acrylic resin 20 parts (Dyanal (registered trademark) BR-87 Mitsubishi Chemical Corporation)
・Methyl ethyl ketone 40 parts ・Toluene 40 parts

(Creation of thermal transfer image receiving sheet 5)
Coating liquid 3 for separation auxiliary layer was changed to coating liquid 4 for separation auxiliary layer having the following composition to form a separation auxiliary layer with a thickness of 5 μm, and a receptive layer was formed on the separation auxiliary layer without forming a durable layer. A thermal transfer image-receiving sheet 5 was obtained in the same manner as the thermal transfer image-receiving sheet 4 except that .

<Coating liquid 4 for separation auxiliary layer>
・Dextrin 5 parts (HiCoaster (registered trademark) PC-11 Sanwa Starch Industries Co., Ltd.)
・Polyethylene glycol 5 parts (PEG4000 Sanyo Chemical Industries, Ltd.)
・Wednesday 90 parts

(Creation of thermal transfer image receiving sheet 6)
Everything was the same as the thermal transfer image-receiving sheet 5, except that the support (2) of the thermal transfer image-receiving sheet 5 was changed to a support (3) made of white base paper (uncoated paper, thickness 150 μm (Mitsubishi Paper Mills, Ltd.)). A thermal transfer image-receiving sheet 6 was obtained.

(Creation of thermal transfer image receiving sheet 7)
Coating liquid 2 for receptor layer having the above composition was applied to a 4 μm thick polyethylene terephthalate film (E5101 Toyobo Co., Ltd.) having a thickness of 25 μm and having the above composition applied to the easily adhesive treated side of the polyethylene terephthalate film (E5101 Toyobo Co., Ltd.). A receptor layer was formed by coating and drying to obtain a thermal transfer image-receiving sheet 7.

(Decorative sheets of Examples 1 to 3, 5 to 9, Comparative Example 1)
The combinations of the thermal transfer sheet and thermal transfer image-receiving sheet prepared above are shown in Table 1 below, and using a printer (DS-620 Dai Nippon Printing Co., Ltd.), the thermal transfer sheet is applied to the receiving layer of the thermal transfer image-receiving sheet. An image is formed using a yellow dye layer, a magenta dye layer, and a cyan dye layer, and the aqueous adhesive layer of the thermal transfer sheet is transferred together with the heat seal layer onto this image. Decorative sheets of Examples 1 to 3, 5 to 9, and Comparative Example 1 were obtained in which a sealing layer and an aqueous adhesive layer were provided in this order. In Comparative Example 1, the transfer layer A was transferred together with the heat seal layer instead of the aqueous adhesive layer.

(Decorative sheet of Example 4)
As shown in Table 1 below, the thermal transfer sheet 6 and the thermal transfer image-receiving sheet 7 prepared above were combined, and a yellow dye layer and a magenta dye layer of the thermal transfer sheet were added to the receiving layer of the thermal transfer image-receiving sheet using a printer (HDP5000 FARGO). , an image is formed using the cyan dye layer, and the aqueous adhesive layer of the thermal transfer sheet is transferred together with the heat seal layer onto this image, and the power is turned off before being retransferred to the card, and the image is formed from within the printer. The decorative sheet of Example 4 was obtained in which a heat seal layer and an aqueous adhesive layer were provided in this order on the image-formed thermal transfer image-receiving sheet.

(Quality evaluation of decorative sheets)
The decorative sheets of each Example and Comparative Example 1 were visually confirmed, and the quality of the decorative sheets was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2.

"Evaluation criteria"
A: An image is formed without any problems.
B: The image is not formed uniformly and has unevenness and roughness.
NG: Image cannot be formed.

(Creation of decorations)
The decorative sheet of each Example and Comparative Example 1 is trimmed by cutting along the outer edge of the image formed on the receiving layer, and the decorative sheet of each Example and Comparative Example 1 after trimming is removed from the decorative sheet. The ornaments of each Example and Comparative Example 1 were obtained by integrating the acrylic plate with the acrylic plate as described below.

The decorative sheets of Examples 1 to 3, 9 and Comparative Example 1 were applied to a decorative object with the water-based adhesive layer (transfer layer A in Comparative Example 1) sufficiently wetted with water, and then the separation auxiliary layer, and the support was removed.

The decorative sheet of Example 4 was attached to an object with the aqueous adhesive layer sufficiently wetted with water.

In the decorative sheets of Examples 5 to 7, the water-based adhesive layer was sufficiently wetted with water and attached to the object, and then a water-soaked towel was attached to the object.The surface of the decorative sheet (support side) The separation auxiliary layer was dissolved and the support was removed.

(Quality evaluation of decorative items)
The decorative sheets of each Example and Comparative Example 1 were air-dried after being attached to the decorative object, and then the state of the decorative sheets of each Example and Comparative Example 1 was checked when the surface was rubbed with a finger. The quality of the ornaments was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2.

"Evaluation criteria"
A: The decorative object and the decorative sheet are firmly adhered to each other by the water-based adhesive layer of the decorative sheet, and the surface is not sticky.
B1: The surface is sticky compared to evaluation A, but there is no problem in using it as a decorative sheet.
B2...Compared with evaluation A, the adhesion between the decorative object and the decorative sheet is lower, but there is no problem in using it as a decorative sheet.
NG: There is no adhesion between the decorative object and the decorative sheet, and the decorative sheet falls off from the decorative object.

(Durability evaluation)
In accordance with JIS-L-0849 (2013), a 500 g weight was placed on the image layer side of the decorative article of each example through the test cloth, and the test cloth was reciprocated 50 times using a friction tester. The condition of the image layer side surface was visually checked, and the durability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2. As the friction tester, a dye fastness friction tester (FR-II, manufactured by Suga Test Instruments Co., Ltd.) was used, and as the test cloth, Kanakin No. 3 (JIS-L-0803 (2011)) was used.

"Evaluation criteria"
A...The image has not been deleted.
B: The image is slightly scratched.

10...Thermal transfer sheet 1...Base material 2...Release layer 3...Dye layer 4...Aqueous adhesive layer 5...Heat seal layer 100...Thermal transfer image receiving sheet 50... Support 60... Durable layer 70... Separation auxiliary layer 80... Receptive layer 200... Decorative sheet

Claims (8)

A thermal transfer image-receiving sheet having a receiving layer provided on a support and a thermal transfer sheet having a dye layer provided on a base material are combined, and the sublimable dye contained in the dye layer is transferred to the receiving layer. forming a thermal transfer image on the receiving layer;
forming an aqueous adhesive layer on the receptor layer on which the thermal transfer image is formed,
The aqueous adhesive layer increases adhesiveness by absorbing water, or exhibits adhesiveness by absorbing water ,
The step of forming the aqueous adhesive layer is a step of forming the aqueous adhesive layer by transfer,
The thermal transfer sheet has the dye layer and the water-based adhesive layer provided on the base material in a plane-sequential manner, and the step of forming the thermal transfer image using the thermal transfer sheet, and the water-based adhesive layer. A method for manufacturing a decorative sheet, which includes a step of forming layers . A separation auxiliary layer is provided between the support and the receptor layer of the thermal transfer image-receiving sheet,
When the surface of the separation auxiliary layer on the receptor layer side is the top surface,
The method for manufacturing a decorative sheet according to claim 1, wherein the receiving layer can be separated using the upper surface of the separation auxiliary layer as a separation interface. The method for manufacturing a decorative sheet according to claim 2, wherein a durable layer is provided between the separation auxiliary layer and the receiving layer. The method for manufacturing a decorative sheet according to any one of claims 1 to 3, wherein a thermal transfer sheet having a heat seal layer provided on the aqueous adhesive layer is used. The method for manufacturing a decorative sheet according to claim 4, wherein the heat seal layer contains a colorant. The method for producing a decorative sheet according to any one of claims 1 to 5, wherein the receptor layer contains a component having a hydroxyl group. The receptor layer and the aqueous adhesive layer both contain a component having a hydroxyl group,
Any one of claims 1 to 3, wherein in the step of forming the aqueous adhesive layer, the aqueous adhesive layer is formed such that the receptor layer on which the thermal transfer image is formed is in direct contact with the aqueous adhesive layer. A method for producing a decorative sheet according to item 1. A method for manufacturing a decorative article, the method comprising:
Including the step of integrating the decorative object and the decorative sheet,
The decorative sheet is a decorative sheet manufactured by the method for manufacturing a decorative sheet according to any one of claims 1 to 7,
A method for manufacturing a decorative article, comprising integrating the decorative object and a decorative sheet using water.

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