JP7848578B2 - Laminates for decorative sheets, decorative sheets, decorative transfer sheets, and decorative articles - Google Patents

Description

This disclosure relates to laminates for decorative sheets, decorative sheets, decorative transfer sheets, and decorative articles.

Conventionally, decorated articles, in which the surface of the object to be decorated is adorned with decorative sheets, have been used for various purposes. The manufacturing methods for decorated articles are broadly classified into two types: primary decoration, which is performed simultaneously with molding, and secondary decoration, which is performed after molding.

For primary decoration, methods such as in-mold molding and insert molding are known. For secondary decoration, methods such as three-dimensional surface decoration, also known as the TOM method (Three-Dimensional Overlay Method), are known.

Furthermore, decorative sheets are known to have an image layer on which an image has been formed. Printing methods are one way to form the image. Printing methods can be broadly classified into two types: plated printing and plateless printing. Among these, plateless printing has the advantage of enabling on-demand printing. Examples of plateless printing methods include inkjet recording and thermal transfer recording. Among these, thermal transfer recording is used in various fields because its image formation principle is simple, and it enables miniaturization and cost reduction.

Furthermore, decorative sheets require not only aesthetic appeal but also a pleasant tactile sensation.

One known method for imparting tactile sensation to decorative sheets is to create a textured surface with raised or recessed areas.

Methods for forming uneven surfaces include, for example, mechanical embossing, which mechanically creates uneven surfaces, and chemical embossing, which creates uneven surfaces by partially suppressing the foaming of a foamed resin layer.

For example, Patent Document 1 discloses a technique for forming uneven surfaces on a foamed decorative sheet used in foamed flooring materials, etc., by chemical embossing, although this is not a decorative sheet used for primary or secondary decoration as described above.

Japanese Patent Publication No. 2020-6565

In chemical embossing, a foam-suppressing ink containing a foam-suppressing agent is applied in a pattern to the surface of the foamed resin layer, or a transfer sheet with a patterned foam-suppressing layer is used to transfer the foam-suppressing layer to the surface of the foamed resin layer. The foamed resin layer is then foamed to form a textured surface.

For example, as described in Patent Document 1, the foam-suppressing layer is formed by plate-based printing methods such as gravure printing and offset printing. However, plate-based printing methods have the problem of being time-consuming and costly because they require the creation of printing plates.

This disclosure is made in view of the above circumstances, and its primary purpose is to provide a laminate for decorative sheets and a transfer sheet for decorative purposes that enables the on-demand manufacturing of decorative sheets or decorative articles with high design quality and tactile properties.

One embodiment of this disclosure provides a laminate for decorative sheets, comprising, in this order, a base layer, a foamable resin layer, a patterned foam-suppressing layer, and an image layer having a thermal transfer image, wherein the foam-suppressing layer contains a foam-suppressing agent that is either molten or sublimable.

Another embodiment of this disclosure provides a decorative sheet comprising, in this order, a base layer, a foamed layer, a patterned foam-suppressing layer, and an image layer having a thermal transfer image, wherein the surface on the image layer side has an uneven shape, and the foam-suppressing layer contains a foam-suppressing agent that is molten or sublimable.

Another embodiment of this disclosure provides a decorative transfer sheet having a release support and a transfer layer, wherein the transfer layer has, in order from the release support side, an image layer having a thermal transfer image and a patterned foam suppression layer, and the foam suppression layer is molten.

Another embodiment of this disclosure provides a decorative article comprising, in this order, an object to be decorated, an adhesive layer, and a laminated sheet, wherein the laminated sheet has an uneven surface, and the laminated sheet comprises, in order from the adhesive layer side, a base layer, a foamed layer, a patterned foaming suppression layer, and an image layer having a thermal transfer image, wherein the foaming suppression layer contains a foaming suppressant that is molten or sublimable.

Another embodiment of this disclosure provides a decorative article comprising, in this order, an object to be decorated, a foamed layer, and a laminated sheet, wherein the laminated sheet has an uneven surface, and the laminated sheet comprises, in order from the foamed layer side, a patterned foaming suppression layer and an image layer having a thermal transfer image, and the foaming suppression layer is molten.

This disclosure offers the advantage of providing laminates for decorative sheets and transfer sheets for decorative purposes that enable the on-demand manufacturing of decorative sheets or decorative articles with high design aesthetics and tactile properties.

This is a schematic cross-sectional view illustrating an example of a laminate for decorative sheets in this disclosure. This is a schematic cross-sectional view illustrating an example of a laminate for decorative sheets in this disclosure. This is a process diagram illustrating the manufacturing method of the decorated article in this disclosure. This is a schematic cross-sectional view illustrating an example of a laminate for decorative sheets in this disclosure. This is a schematic cross-sectional view illustrating an example of a decorative sheet in this disclosure. This is a schematic cross-sectional view illustrating an example of a decorative transfer sheet in this disclosure. This is a process diagram illustrating the manufacturing method of the decorated article in this disclosure. This is a process diagram illustrating the manufacturing method of the decorated article in this disclosure. This is a schematic cross-sectional view illustrating an example of a decorative transfer sheet in this disclosure. This is a schematic cross-sectional view illustrating an example of a decorated article in this disclosure. This is a schematic cross-sectional view illustrating an example of a decorated article in this disclosure.

The embodiments of this disclosure will be described below with reference to the drawings and other illustrations. However, this disclosure can be implemented in many different ways, and should not be limited to the embodiments described below. Furthermore, while the drawings may schematically represent the width, thickness, shape, etc., of parts in order to clarify the explanation, these are merely examples and should not be interpreted as limiting. Also, in this specification and the drawings, elements similar to those described above in previously shown drawings are denoted by the same reference numerals, and detailed explanations may be omitted as appropriate.

In this specification, when describing a configuration in which one component is placed on top of another component, unless otherwise specified, the terms "above" or "below" include both cases: the other component being placed directly above or below the component in contact with it, and the other component being placed above or below the component via yet another component. Furthermore, when describing a configuration in this specification in which one component is placed on the surface of another component, unless otherwise specified, the terms "on the surface" or "on the surface" include both cases: the other component being placed directly above or below the component in contact with it, and the other component being placed above or below the component via yet another component.

Furthermore, in this specification, the term "sheet" also includes components referred to as "film."

The laminates for decorative sheets, decorative sheets, decorative transfer sheets, and decorative articles described herein will be explained in detail below.

A. Laminate for decorative sheets The laminate for decorative sheets in this disclosure comprises, in this order, a base layer, a foamable resin layer, a patterned foam suppression layer, and an image layer having a thermal transfer image, and contains a foam suppressant in which the foam suppression layer is molten or sublimable.

Figures 1 and 2 are schematic cross-sectional views illustrating a laminate for decorative sheets in this disclosure. As illustrated in Figures 1 and 2, the laminate for decorative sheets 10 comprises, in this order, a base layer 1, a foamed resin layer 2, a patterned foaming suppression layer 3, and an image layer 4 having a thermal transfer image 14. In the laminate for decorative sheets 10 shown in Figure 1, the foaming suppression layer 3 is molten and is located on the side of the foamed resin layer 2 opposite to the base layer 1. In the laminate for decorative sheets 10 shown in Figure 2, the foaming suppression layer 3 contains a sublimable foaming inhibitor and is located inside the foamed resin layer 2.

In the laminate for decorative sheets described in this disclosure, the image layer has a thermal transfer image, enabling on-demand printing. Furthermore, if the foam suppression layer is molten, it can be formed in a pattern using a molten thermal transfer method. Also, if the foam suppression layer contains a sublimable foam suppressant, it can be formed in a pattern using a sublimation thermal transfer method. Therefore, not only the image layer but also the foam suppression layer can be printed on demand, making it possible to accommodate small-lot, high-mix, and short-lead-time manufacturing.

Furthermore, the decorative sheet laminate described in this disclosure is used for decoration by a bonding method.

Figures 3(a) to 3(c) are process diagrams illustrating a method for manufacturing a decorated article using the decorative sheet laminate described in this disclosure. First, as shown in Figure 3(a), a decorative sheet laminate 10 is prepared. The decorative sheet laminate 10 is the same as the decorative sheet laminate 10 shown in Figure 1. Next, as shown in Figures 3(a) to 3(b), the foamed resin layer 2 is foamed to form a foamed layer 12. This yields a decorative sheet 20 having an uneven surface. Next, as shown in Figure 3(c), the decorative sheet 20 and the object to be decorated 31 are positioned so that the surface of the decorative sheet 20 facing the base material layer 1 faces the object to be decorated 31, and they are integrated via an adhesive layer 32. This yields a decorated article 30 having an uneven surface.

In areas where the foam-suppressing layer is present, the foaming of the foamable resin layer is suppressed by the foam-suppressing agent contained in the layer. Therefore, the areas with the foam-suppressing layer become concave, while areas without the foam-suppressing layer become convex. This creates an uneven surface on the decorative sheet and decorative article.

In this embodiment, a patterned foaming suppression layer is arranged between the foaming resin layer and the image layer. Because the foaming resin layer and the foaming suppression layer are located close together, the foaming suppression effect can be enhanced.

The following describes the various components of the laminate for decorative sheets in this disclosure.

1. Foam-suppressing layer The foam-suppressing layer in this disclosure is a member arranged in a pattern. The foam-suppressing layer has two embodiments. Each embodiment will be described below.

(1) Foam suppression layer of the first embodiment The foam suppression layer of this embodiment is meltable. Because the foam suppression layer is meltable, the foam suppression layer can be formed in a pattern on the surface of the foamed resin layer opposite to the base layer by a melt-type heat transfer method.

In this embodiment, as described above, the foam suppression layer is molten, and the foam suppression layer is formed in a pattern on the side of the foamed resin layer opposite to the base layer by a molten heat transfer method. In the molten heat transfer method, a laminate having a base layer and a foamed resin layer, and a molten heat transfer sheet having a foam suppression layer are used. Thermal energy corresponding to the information of the uneven shape is applied to the molten heat transfer sheet, and the foam suppression layer, melted or softened by the application of thermal energy, is transferred layer by layer to the foamed resin layer side of the laminate, thereby forming a pattern of foam suppression layer.

Therefore, in order to suppress foaming of the foamable resin layer during the thermal transfer of the foam-suppressing layer, it is preferable that the melting start temperature of the foam-suppressing layer be lower than the foaming temperature of the foamable resin layer. Specifically, the melting start temperature of the foam-suppressing layer is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 100°C or lower.

Here, the melting onset temperature refers to the temperature at which the endothermic peak rises from the baseline in the DSC curve obtained by differential scanning calorimetry (DSC).

Furthermore, the foaming temperature of the foamed resin layer can be considered as the foaming temperature of the foaming agent contained in the foamed resin layer. If the foaming agent is a thermal decomposition type foaming agent, the foaming temperature of the foaming agent refers to the decomposition temperature of the thermal decomposition type foaming agent.

The foam-inhibiting layer contains a foam inhibitor and a molten resin.

As a foaming inhibitor, a general foaming inhibitor can be used, and it should be selected appropriately depending on the type of foaming agent and resin contained in the foamed resin layer.

In particular, to suppress the vaporization of the foam inhibitor during the thermal transfer of the foam-inhibiting layer, it is preferable that the boiling point or sublimation point of the foam inhibitor be higher than the melting initiation temperature of the foam-inhibiting layer. Specifically, it is preferable that the boiling point or sublimation point of the foam inhibitor be 200°C or higher.

In this specification, boiling point refers to the boiling point at 1 atmosphere. Similarly, sublimation point refers to the sublimation point at 1 atmosphere.

Examples of foam inhibitors include trimellitic anhydride, maleic acid, fumaric acid, adipic acid, triazine compounds, and triazole compounds. Examples of triazole compounds include benzotriazole compounds and aminotriazole compounds. These may be used individually or in combination of two or more. Among these, triazole compounds are preferred, and aminotriazole compounds are more preferred.

The content of the foaming inhibitor in the foaming inhibitor layer is not particularly limited as long as a foaming inhibitory effect is obtained when the foaming resin layer is foamed. For example, it may be 5% by mass or more and 50% by mass or less, or 10% by mass or more and 40% by mass or less.

The resin contained in the foam suppression layer is not particularly limited as long as it is a molten resin; for example, a thermoplastic resin can be used. As the thermoplastic resin, a general thermoplastic resin used in the molten inks of molten-type thermal transfer sheets can be used.

In particular, to suppress foaming of the foamable resin layer during the thermal transfer of the foam-suppressing layer, it is preferable that the melting start temperature of the thermoplastic resin is lower than the foaming temperature of the foamable resin layer.

Examples of thermoplastic resins include polyolefin resins, ethylene copolymers, vinyl chloride resins, vinylidene chloride resins, styrene resins, methacrylic acid ester copolymers, vinyl acetate resins, vinyl butyral resins, polyamide resins, polyethylene glycol, and cellulose derivatives. Examples of polyolefin resins include polyethylene and polypropylene. Examples of ethylene copolymers include ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, and ethylene-acrylic acid copolymers. Examples of vinyl chloride resins include polyvinyl chloride and vinyl chloride-vinyl acetate copolymers. Examples of vinylidene chloride resins include polyvinylidene chloride and vinylidene chloride copolymers. Examples of styrene resins include polystyrene. Examples of methacrylic acid ester copolymers include polymethacrylic acid ester copolymers, methyl methacrylate-vinyl acetate copolymers, and methyl methacrylate-acrylic acid copolymers. Examples of vinyl acetate resins include polyvinyl acetate and vinyl acetate copolymers. Examples of polyamide resins include nylon, copolymerized nylon, and N-alkoxymethylated nylon. These can be used individually or in combination of two or more types.

Furthermore, the foam-suppressing layer may contain wax. By including wax in the foam-suppressing layer, the melting start temperature of the foam-suppressing layer can be lowered, even when the melting start temperature of the thermoplastic resin is relatively high.

The wax content in the foam-suppressing layer is appropriately selected depending on the foaming agent content, etc. For example, the wax content in the foam-suppressing layer may be 0.5% by mass or more and 15% by mass or less.

Furthermore, the foam suppression layer may contain a coloring agent. In this case, the foam suppression layer and the image layer can be easily synchronized.

The foam-suppressing layer may contain additives as needed.

The thickness of the foam-suppressing layer is not particularly limited, as long as it is a thickness that provides a foam-suppressing effect when the foamable resin layer is foamed. For example, it may be 0.1 μm or more and 50.0 μm or less, 0.5 μm or more and 10.0 μm or less, or 1.0 μm or more and 5.0 μm or less.

The foam-suppressing layer is arranged in a pattern. In plan view, the pattern shape of the foam-suppressing layer is not particularly limited. Examples include lines, dots, and grids. In the case of a dot pattern, the planar shape of the dots may be, for example, circular, elliptical, triangular, or rectangular.

The preferred method for forming the foam-suppressing layer is a molten heat transfer method. When the foam-suppressing layer is heat-transferred using the molten heat transfer method, the foamable resin layer is subjected to heat and pressure from the thermal head. The heating temperature of the thermal head is preferably lower than the foaming temperature of the foamable resin layer. This suppresses foaming of the foamable resin layer during the heat transfer of the foam-suppressing layer.

(2) Foam-suppressing layer of the second embodiment The foam-suppressing layer of this embodiment contains a foam-suppressing agent that has sublimation properties. By containing a foam-suppressing agent that has sublimation properties, the foam-suppressing layer can be formed in a pattern inside the foamable resin layer by a sublimation-type thermal transfer method.

The foam-suppressing layer contains a foam-suppressing agent that exhibits sublimation properties.

In this embodiment, as described above, the foaming inhibition layer contains a sublimable foaming inhibitor, thereby forming a patterned foaming inhibition layer within the foamed resin layer using a sublimation-type thermal transfer method. The sublimation-type thermal transfer method utilizes a laminate having a base layer and a foamed resin layer, and a sublimation-type thermal transfer sheet having a foaming inhibition layer containing a sublimable foaming inhibitor. Thermal energy corresponding to the information of the uneven surface is applied to the sublimation-type thermal transfer sheet, transferring the sublimable foaming inhibitor contained in the foaming inhibition layer to the foamed resin layer of the laminate, thereby forming a patterned foaming inhibition layer.

Therefore, in order to suppress foaming of the foaming resin layer during the thermal transfer of the foaming inhibitor, it is preferable that the sublimation point of the foaming inhibitor is lower than the foaming temperature of the foaming resin layer. Specifically, the sublimation point of the foaming inhibitor may be 130°C or lower, 120°C or lower, or 110°C or lower.

Any foaming inhibitor with sublimation properties can be used as the foaming inhibitor; general foaming inhibitors can be used and selected appropriately depending on the type of foaming agent and resin contained in the foamed resin layer. In particular, it is preferable that the foaming inhibitor satisfies the above-mentioned sublimation point.

Examples of foam inhibitors include triazole compounds. Foam inhibitors may be used alone or in combination of two or more.

The preferred method for forming the foam-suppressing layer is a sublimation-type thermal transfer method. When the foam-suppressing layer is thermally transferred using the sublimation-type thermal transfer method, the foamable resin layer is subjected to heat and pressure from the thermal head. It is preferable that the heating temperature of the thermal head be lower than the foaming temperature of the foamable resin layer. This suppresses foaming of the foamable resin layer during the thermal transfer of the foam-suppressing layer.

The foam-suppressing layer is arranged in a pattern. The pattern shape of the foam-suppressing layer in a plan view is the same as the pattern shape of the foam-suppressing layer in the first embodiment described above.

2. Image Layer The image layer in this disclosure has a thermal transfer image.

The thermal transfer image may be a thermal transfer image formed by a sublimation thermal transfer method or a thermal transfer image formed by a melt thermal transfer method. Furthermore, the image layer may have a first image layer having a thermal transfer image formed by a sublimation thermal transfer method and a second image layer having a thermal transfer image formed by a melt thermal transfer method. In this case, the stacking order of the first and second image layers is not particularly limited. The image layer may have a first image layer and a second image layer, or a second image layer and a first image layer, in order from the foam suppression layer side. For example, in Figure 4, the image layer 4 has a first image layer 4a having a thermal transfer image 14a formed by a sublimation thermal transfer method, and a second image layer 4b having a thermal transfer image 14b formed by a melt thermal transfer method, in order from the foam suppression layer 3 side.

(1) Sublimation Thermal Transfer Method The sublimation thermal transfer method is a method in which thermal energy corresponding to the image information is applied to the sublimation thermal transfer sheet, and the sublimation dye contained in the colorant layer is transferred to the receiving layer of the laminate, thereby forming a thermal transfer image.

Therefore, an image layer having a thermal transfer image formed by a sublimation thermal transfer method is a receiving layer having a thermal transfer image containing a sublimable dye.

The receiving layer is a layer capable of receiving sublimation dyes. The receiving layer contains components capable of receiving sublimation dyes. As the components capable of receiving sublimation dyes, general receiving layer materials used in thermal transfer image receiving sheets can be used. These components may be used individually or in combination of two or more.

For sublimation dyes, general sublimation dyes used in heat transfer sheets can be used.

The method for forming the receptive layer is not particularly limited. Examples include applying a coating solution containing the receptive layer material, or transferring the receptive layer using a transfer sheet having the receptive layer. In the case of the transfer method, it may be thermal transfer or non-heating transfer.

A general-purpose dye-sublimation thermal transfer sheet can be used as the sheet used to form the image layer.

The sublimation-type thermal transfer sheet comprises a support layer and a colorant layer disposed on one side of the support layer, containing a sublimable dye and resin.

To suppress foaming of the foamed resin layer during the formation of a thermal transfer image, it is preferable that the glass transition temperature (Tg) of the resin contained in the colorant layer of the sublimation thermal transfer sheet be lower than the foaming temperature of the foamed resin layer. Specifically, the glass transition temperature is preferably between 100°C and 130°C.

In a sublimation thermal transfer sheet, one type of colorant layer may be arranged on one side of the support layer, or multiple types of colorant layers with different colors may be arranged planarly.

(2) Melt-type thermal transfer method The melt-type thermal transfer method uses a laminate having a base layer, a foaming resin layer, and a patterned foam suppression layer in that order, and a melt-type thermal transfer sheet having a melt-ink layer containing melt-ink. Thermal energy corresponding to the image information is applied to the melt-type thermal transfer sheet, and the melt-ink layer, which has been melted or softened by the application of thermal energy, is transferred layer by layer to the foam suppression layer side of the laminate, thereby forming a thermal transfer image.

Therefore, the image layer containing the thermal transfer image formed by the molten thermal transfer method is a molten ink layer.

To suppress foaming of the foamed resin layer during the formation of the thermal transfer image, the melting start temperature of the molten ink layer is preferably lower than the foaming temperature of the foamed resin layer. Specifically, the melting start temperature of the molten ink layer is preferably 130°C or lower, more preferably 120°C or lower, and even more preferably 100°C or lower.

The molten ink layer contains molten ink. The molten ink contains a colorant and a molten resin.

Examples of colorants include pigments and dyes. The color of the colorant is not particularly limited. Pigments may include, for example, metallic pigments or pearl pigments.

The resin used is not particularly limited as long as it is a molten resin; for example, thermoplastic resins can be used. As the thermoplastic resin, general thermoplastic resins used in the molten inks of molten-type thermal transfer sheets can be used.

In particular, to suppress foaming of the foamed resin layer during the formation of the thermal transfer image, it is preferable that the melting start temperature of the thermoplastic resin is lower than the foaming temperature of the foamed resin layer.

Specific examples of thermoplastic resins are the same as those used in the foam-suppressing layer described above.

The molten ink layer may contain wax. By including wax in the molten ink layer, the melting start temperature of the molten ink layer can be lowered, even when the melting start temperature of the thermoplastic resin is relatively high.

The content of each component in the molten ink layer is set appropriately, taking into consideration factors such as the density of the thermal transfer image and the shelf life of the molten thermal transfer sheet.

A general-purpose fused-type thermal transfer sheet can be used as the fused-type thermal transfer sheet used to form the image layer.

3. Foamed resin layer The foamed resin layer in this disclosure contains a foaming agent and a resin.

The foaming agent is preferably a thermal decomposition type foaming agent. In this case, when the foamed resin layer is heated, the thermal decomposition type foaming agent decomposes and generates gas, forming the foamed layer. At this time, in the region where the foaming suppression layer is located, the foaming inhibitor contained in the foaming suppression layer suppresses the decomposition of the thermal decomposition type foaming agent contained in the foamed resin layer. Therefore, an uneven surface can be formed on the foaming suppression layer side of the foamed layer.

As a thermal decomposition type blowing agent, general thermal decomposition type blowing agents can be used. Examples include organic thermal decomposition type blowing agents and inorganic thermal decomposition type blowing agents. Examples of organic thermal decomposition type blowing agents include azo compounds, hydrazine derivatives, and nitroso compounds. Examples of azo compounds include azodicarbonamide (ADCA). Examples of hydrazine derivatives include oxybisbenzenesulfonyl hydrazide (OBSH). Examples of nitroso compounds include dinitrosopentamethylenetetramine (DPT). Examples of inorganic thermal decomposition type blowing agents include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, and ammonium nitrite. These may be used individually or in combination of two or more.

Furthermore, in the case of thermal decomposition type foaming agents, since the foaming resin layer is foamed by heating, considering the heat resistance of the base layer, it is preferable that the decomposition temperature of the thermal decomposition type foaming agent be lower than the softening point of the base layer.

Furthermore, when the image layer contains a thermal transfer image formed by a sublimation thermal transfer method, it is preferable that the decomposition temperature of the thermal decomposition foaming agent be relatively low. If the decomposition temperature of the thermal decomposition foaming agent is too high, the diffusion of the sublimable dye contained in the thermal transfer image can be suppressed when the foaming resin layer is foamed by heating. This suppresses blurring of the thermal transfer image.

Specifically, the decomposition temperature of the thermal decomposition type blowing agent is preferably 140°C to 230°C, more preferably 150°C to 200°C, and even more preferably 150°C to 180°C.

Here, the decomposition temperature of a pyrolytic blowing agent can be measured by thermogravimetric analysis (TG). Specifically, the decomposition temperature of a pyrolytic blowing agent is the temperature at which weight loss begins in the TG curve, i.e., the decomposition initiation temperature.

The amount of foaming agent can be appropriately set depending on the type of foaming agent, the foaming ratio, etc. For example, the amount of foaming agent may be, for example, 1 part by mass or more and 20 parts by mass per 100 parts by mass of resin, or it may be 3 parts by mass or more and 10 parts by mass or less.

The resin is not particularly limited and includes, for example, vinyl chloride resin, olefin resin, polystyrene resin, polyvinyl acetate, polyurethane, polytetrafluoroethylene, ABS resin (acrylonitrile-styrene-butadiene copolymer), acrylic resin, polyamide, polyacetal, polycarbonate, polyester, polyphenylene sulfide, and polyetheretherketone. These may be used individually or in combination of two or more. Among these, vinyl chloride resin is preferred.

The foamed resin layer may contain a foaming aid. The foaming aid acts to accelerate the decomposition of the thermally decomposed foaming agent, lower the decomposition temperature of the thermally decomposed foaming agent, and homogenize the foamed bubbles. General foaming aids can be used, and are appropriately selected depending on the type of thermally decomposed foaming agent. Examples of foaming aids include metal oxides, fatty acid metal salts, urea-based aids, and organic acids. These may be used individually or in combination of two or more.

The amount of foaming agent is not particularly limited; for example, it may be 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of resin, or it may be 0.01 parts by mass or more and 5 parts by mass or less.

The foamed resin layer may contain inorganic fillers for purposes such as imparting flame retardancy, suppressing pores, and improving surface strength. The inorganic fillers are not particularly limited and include, for example, calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compounds, and titanium dioxide. These may be used individually or in combination of two or more.

The content of the inorganic filler is not particularly limited, but for example, it may be 0 to 100 parts by mass, or 20 to 70 parts by mass, per 100 parts by mass of resin.

Furthermore, the foamed resin layer may contain additives such as antifungal agents, pigments, antioxidants, light stabilizers, crosslinking agents, crosslinking aids, foaming aids, insecticides, preservatives, antibacterial agents, diluents, deodorizers, and plasticizers, as needed.

The thickness of the foamed resin layer is not particularly limited; for example, it may be 30 μm or more and 300 μm or less, or 50 μm or more and 150 μm or less.

Methods for forming a foamed resin layer include, for example, applying a foamed resin composition containing a foaming agent and resin onto a substrate layer; extruding and laminating the foamed resin composition onto a substrate layer; and forming a pre-film-like foamed resin layer and then laminating it onto a substrate layer.

4. Substrate Layer The substrate layer in this disclosure is a member that supports the foamed resin layer, the foaming suppression layer, and the image layer.

When decorating a three-dimensional object using a decorative sheet laminate, for example, the foamed resin layer of the decorative sheet laminate can be foamed to obtain a decorative sheet, and then the decorative sheet can be stretched and bonded to the surface of the object to be decorated. Therefore, it is preferable that the base layer has stretchability. Specifically, it is preferable that the elongation rate of the base layer at 130°C is 200% or more. Having the above elongation rate within this range improves the stretchability of the decorative sheet laminate and the decorative sheet, and enhances the moldability of the decorative sheet. On the other hand, the upper limit of the elongation rate of the base layer at 130°C is not particularly limited, but for example, it is 500% or less.

Here, the elongation of the base layer at 130°C can be measured by a test method compliant with JIS K7127:1999. Specifically, in accordance with JIS K7127:1999, a tensile testing machine is used to pull the test specimen at a temperature of 130°C and a speed of 200 mm/min. The elongation of the test specimen at which it breaks (fractures) is defined as the elongation of the base layer at 130°C. The elongation at 130°C is calculated using the following formula (1). For example, a Tensilon universal material tester can be used as a tensile testing machine.

Growth rate (%) = 100 × (L - L ₀ ) / L ₀ (1)
(In the above formula (1), _L0 is the length of the specimen before the test, and L is the length of the specimen at the time of fracture.)

Furthermore, as mentioned above, when using a thermal decomposition type foaming agent in the foamed resin layer, since the foamed resin layer is foamed by heating, it is preferable that the softening point of the base layer be higher than the decomposition temperature of the thermal decomposition type foaming agent, considering the heat resistance of the base layer.

A resin film can be used as the base layer. In particular, the base layer is preferably a resin film that satisfies the above-mentioned elongation rate at 130°C. Examples of resin films include thermoplastic resin films. Examples of thermoplastic resins constituting the thermoplastic resin film include acrylic resins, vinyl chloride resins, ABS resins (acrylonitrile-styrene-butadiene copolymers), styrene resins, polycarbonate resins, polyester resins, polyolefin resins, and urethane resins. Examples of polyester resins include polyethylene terephthalate (PET) and glycol-modified polyethylene terephthalate (PET-G). Examples of polyolefin resins include polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and olefin-based thermoplastic elastomers.

The base layer may contain various additives as needed. Examples of additives include stabilizers, plasticizers, colorants, UV absorbers, light stabilizers, and extender pigments.

The base layer may be a single-layer structure or a laminated structure.

The thickness of the base layer is preferably such that it satisfies the elongation rate at 130°C, for example, 25 μm to 450 μm, 30 μm to 300 μm, or 50 μm to 200 μm. When the thickness of the base layer is within this range, trimming of the excess portion of the decorative sheet after integrating the decorative sheet with the object to be decorated becomes easier. On the other hand, if the thickness of the base layer is too thick, depending on the material of the base layer, it may not satisfy the elongation rate at 130°C.

5. Protective Layer The decorative sheet laminate in this disclosure may have a protective layer 5 on the side of the image layer 4 opposite to the foam suppression layer 3, as shown in Figure 4, for example. In a decorative article using the decorative sheet laminate, the protective layer is a member that protects the image layer and the foam layer. The protective layer can also provide scratch resistance. Furthermore, if the foam suppressant contained in the foam suppression layer is sublimable, the protective layer can suppress the decrease of the foam suppressant in the foam suppression layer. This can suppress a decrease in the foam suppression effect.

The protective layer may be a single-layer structure or a multi-layer structure. In the case of a multi-layer structure, layers with different functions may be laminated.

The material for the protective layer is not particularly limited, and examples include thermoplastic resins and curable resins.

If the protective layer contains a curable resin, it is preferable to include a curable resin composition containing the curable resin. Examples of curable resin compositions include thermosetting resin compositions and ionizing radiation-curable resin compositions. Among these, ionizing radiation-curable resin compositions are preferred.

A thermosetting resin composition is a composition containing at least a thermosetting resin, which hardens upon heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. A curing agent may be added to the thermosetting resin composition as needed.

An ionizing radiation-curable resin composition is a composition containing an ionizing radiation-curable resin. The ionizing radiation-curable resin has ionizing radiation-curable functional groups. Examples of ionizing radiation-curable functional groups include ethylenically unsaturated bonding groups, epoxy groups, and oxetanyl groups. Examples of ethylenically unsaturated bonding groups include (meth)acryloyl groups, vinyl groups, and allyl groups.

Ionizing radiation refers to electromagnetic waves or charged particle beams that possess energy quanta capable of polymerizing or crosslinking molecules. Typically, ultraviolet (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams can also be used.

Ionizing radiation-curable resins can be monomers, oligomers, or polymers.

Examples of ionizing radiation-curable resins include acrylic (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate. Among these, urethane (meth)acrylate is preferred. Ionizing radiation-curable resins may be used individually or in mixtures of two or more types.

Furthermore, the ionizing radiation-curable composition may further contain a polyfunctional isocyanate.

A polyfunctional isocyanate is a compound having two or more isocyanate groups. Examples of polyfunctional isocyanates include aromatic isocyanates and aliphatic isocyanates. Examples of aromatic isocyanates include 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4-diphenylmethane diisocyanate. Examples of aliphatic isocyanates include 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Adducts or polymers of these various isocyanates, as well as blocked isocyanate compounds, can also be used. Examples of isocyanate adducts and polymers include tolylene diisocyanate adducts and tolylene diisocyanate trimers.

In particular, polyfunctional isocyanates are preferably those having ionizing radiation-curable functional groups. Especially preferred are polyfunctional isocyanates having two or more isocyanate groups and one or more ethylenically unsaturated bonding groups. This can increase the hardness of the hard coat layer.

The ionizing radiation-curable composition may contain a photopolymerization initiator. The photopolymerization initiator can be appropriately selected from a range of common photopolymerization initiators. The photopolymerization initiator may be used alone or in combination with others.

The content of the photopolymerization initiator is, for example, 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the ionizing radiation-curable resin, and may be 1 part by mass or more and 8 parts by mass or 3 parts by mass or more and 8 parts by mass.

Ionizing radiation-curable compositions may contain various additives depending on the desired properties. Examples of additives include ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, defoamers, and fillers.

The thickness of the protective layer may be, for example, 0.5 μm to 30 μm, 1 μm to 20 μm, or 3 μm to 10 μm.

The method for forming the protective layer is not particularly limited. Examples include applying a resin composition containing a thermoplastic resin or a curable resin, or transferring the protective layer using a transfer sheet having a protective layer. In the case of the transfer method, it may be a thermal transfer or a non-heating transfer. Furthermore, when the protective layer contains a curable resin composition, it is preferable to cure the protective layer after integrating the decorative sheet and the object to be decorated. This helps to suppress cracking of the protective layer when integrating the decorative sheet and the object to be decorated.

6. Antistatic Layer The decorative sheet laminate in this disclosure may have an antistatic layer 6 on the surface of the base layer 1 opposite to the foamed resin layer 2, as shown in Figure 4, for example. The antistatic layer is a component provided to suppress the adhesion of foreign matter to the decorative sheet laminate.

For the antistatic layer, general antistatic agents can be used. Examples of such antistatic agents include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, inorganic conductive materials such as carbon and metals, and conductive polymers.

The thickness of the antistatic layer is, for example, 0.1 μm to 5 μm.

One method for forming an antistatic layer is to apply a composition containing an antistatic agent onto a substrate layer.

7. Anchor Layer The laminate for decorative sheets in this disclosure may have an anchor layer 7 between the base layer 1 and the foamed resin layer 2, for example, as shown in Figure 4. The anchor layer can improve the adhesion between the base layer and the foamed resin layer.

Examples of anchor layer materials include acrylic resins, vinyl chloride resins, vinyl acetate resins, polyester resins, and urethane resins.

Furthermore, the anchor layer may contain additives such as UV absorbers and light stabilizers.

In particular, the anchor layer preferably contains an ultraviolet absorber. This can improve the lightfastness of the thermal transfer image in the image layer. Especially when curing the protective layer or the adhesive layer with ultraviolet light, it can suppress the degradation of the thermal transfer image due to ultraviolet light. A general-purpose ultraviolet absorber can be used as the ultraviolet absorber.

The thickness of the anchor layer is not particularly limited; for example, it may be between 0.1 μm and 10 μm.

8. Intermediate Layer The laminate for decorative sheets in this disclosure may have an intermediate layer containing an ultraviolet absorber between the image layer and the protective layer. This can improve the light resistance of the thermal transfer image of the image layer. In particular, when the protective layer is cured by ultraviolet light, the degradation of the thermal transfer image due to ultraviolet light can be suppressed.

The intermediate layer contains a UV absorber and a resin.

For the UV absorber, a general-purpose UV absorber can be used.

The resin is not particularly limited and examples include acrylic resin, polyester, polyurethane, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyvinylpyrrolidone, and polyvinyl alcohol. These materials may be used individually or in combination of two or more.

The thickness of the intermediate layer is, for example, between 0.01 μm and 5 μm.

The method for forming the intermediate layer is not particularly limited. Examples include applying a coating solution containing the intermediate layer material, or transferring the intermediate layer using a transfer sheet having an intermediate layer. In the case of the transfer method, it may be thermal transfer or non-heating transfer.

9. Adhesive Layer The laminate for decorative sheets in this disclosure may have an adhesive layer 32 on the side of the base layer 1 opposite to the foamed resin layer 2, as shown in Figure 4, for example. The adhesive layer is a component for bonding the decorative sheet to the object to be decorated.

Examples of adhesives that can be used in the adhesive layer include pressure-sensitive adhesives, curing adhesives, and heat-melt adhesives.

In particular, the adhesive is preferably one that has initial tackiness. This enhances the adhesion between the decorative sheet and the object being decorated when integrating them.

Furthermore, the adhesive layer may contain a tackifier resin. This can improve adhesion to the object being decorated. The tackifier resin is also called a tackifier. A suitable tackifier resin can be selected from a range of common tackifier resins. The tackifier resin may be used alone or in combination of two or more types.

The thickness of the adhesive layer is appropriately selected depending on the decoration method of the object to be decorated. For example, it may be 10 μm or more and 100 μm or less, 30 μm or more and 95 μm or less, or 50 μm or more and 85 μm or less.

The method for forming the adhesive layer is not particularly limited and includes, for example, applying an adhesive composition, using a transfer sheet with an adhesive layer to transfer the adhesive layer, or using an adhesive film and laminating the adhesive film. In the case of the transfer method, it may be thermal transfer or non-heating transfer. Furthermore, if the adhesive layer is curable, the adhesive layer is cured after the decorative sheet and the object to be decorated are integrated. The curing method for the adhesive layer is appropriately selected depending on the type of adhesive and includes, for example, irradiation with ionizing radiation, irradiation with visible light, or heating.

B. Decorative Sheet The decorative sheet in this disclosure comprises, in this order, a base layer, a foamed layer, a patterned foaming suppression layer, and an image layer having a thermal transfer image, the surface on the image layer side having an uneven shape, and the foaming suppression layer contains a foaming suppressant that is molten or sublimable.

Figure 5 is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. As illustrated in Figure 5, the decorative sheet 20 comprises, in this order, a base layer 1, a foamed layer 12, a patterned foaming suppression layer 3, and an image layer 4 having a thermal transfer image 14, with an uneven surface on the image layer 4 side. In the decorative sheet 10, the foaming suppression layer 3 contains a foaming suppressant that is molten or sublimable.

The decorative sheet in this disclosure can be obtained by foaming the foamed resin layer in the laminate for decorative sheets described above. Therefore, the decorative sheet in this disclosure exhibits the same effects as the laminate for decorative sheets described above.

The following describes the various components of the decorative sheet in this disclosure.

1. Uneven Shape The decorative sheet in this disclosure has an uneven shape on the surface facing the image layer.

The cross-sectional shape of the uneven surface is not particularly limited.

Furthermore, the planar shape of the uneven surface is not particularly limited. The planar shape of the uneven surface may, for example, be linear or dotted. Examples of dotted planar shapes include circular, elliptical, triangular, and rectangular shapes.

Examples of textured patterns include wood grain grooves, stone surface irregularities, fabric surface textures, pearlescent finishes, sand textures, hairline finishes, and fine grooves, and combinations of these are also acceptable.

2. Foamed Layer The foamed layer in this disclosure has air bubbles inside. The air bubbles may be closed cells, open cells, or a mixture of closed and open cells. Furthermore, the number, size, density, shape, etc. of the air bubbles are not particularly limited and can be appropriately designed according to the type and application of the decorative article. The air bubbles can be formed by foaming the foaming agent contained in the foamed resin layer of the laminate for decorative sheets described above.

The foamed layer preferably contains at least one of the resin and its crosslinked product as a resin component. The crosslinked product is a crosslinked product formed by crosslinking the molecular chains of the resin. For example, it may be a crosslinked product formed by electron beam irradiation, or a crosslinked product formed by a crosslinking agent.

The resin is the same as the resin used in the foamed resin layer of the laminate for decorative sheets described above.

The foamed layer may contain an inorganic filler. The inorganic filler is the same as the inorganic filler used in the foamed resin layer of the laminate for decorative sheets described above.

The foamed layer may contain additives such as fungicides, pigments, antioxidants, light stabilizers, crosslinking agents, crosslinking aids, foaming aids, insecticides, preservatives, antibacterial agents, diluents, deodorizers, and plasticizers, as needed. It may also contain unfoamed foaming agents.

The foamed layer has an uneven surface on the side facing the foaming inhibition layer. In the foamed layer, the areas where the foaming inhibition layer is located are recessed, while the areas where the foaming inhibition layer is not located are convex. The depth of the recesses is preferably, for example, 50 μm to 400 μm.

In the foamed layer, the thickness of the region where the foam-suppressing layer is not present is not particularly limited, but for example, it may be 200 μm or more and 1500 μm or less, or 500 μm or more and 1200 μm or less.

The foamed layer can be formed by heating and foaming the foamed resin layer in the laminate for decorative sheets described above. The heating temperature and heating time are appropriately set according to the type of foaming agent and the thickness of the foamed resin layer.

3. Other Configurations In the decorative sheet described herein, the configurations other than the foam layer are the same as those of the laminate for decorative sheets described above.

C. Decorative Transfer Sheet The decorative transfer sheet in this disclosure is a decorative transfer sheet having a release support and a transfer layer, wherein the transfer layer has, in order from the release support side, an image layer having a thermal transfer image and a patterned foam suppression layer, and the foam suppression layer is meltable.

Figure 6 is a schematic cross-sectional view illustrating a decorative transfer sheet in this disclosure. As illustrated in Figure 6, the decorative transfer sheet 40 comprises a release support 41 and a transfer layer 42. The transfer layer 42, starting from the release support 41 side, comprises an image layer 4 having a thermal transfer image 14 and a patterned foaming suppression layer 3. In the decorative transfer sheet 40, the foaming suppression layer 3 is molten and is located on the side of the image layer 4 opposite to the release support 41.

In the decorative transfer sheet described herein, the image layer has a heat-transfer image, enabling on-demand printing. Furthermore, because the foam suppression layer is molten, it can be formed in a patterned manner using a melt-type heat transfer method. Therefore, both the image layer and the foam suppression layer can be printed on demand, making it possible to accommodate small-lot, high-mix, and short-lead-time manufacturing.

Furthermore, the decorative transfer sheet described in this disclosure is used for decoration by a transfer method. In the decorative transfer sheet, the component located on the image layer side of the release support becomes the transfer layer.

Figures 7(a) to 7(c) and 7(c) and 7(c) are process diagrams illustrating a method for manufacturing a decorated article using a decorative transfer sheet according to this disclosure. First, as shown in Figure 7(a), a decorative transfer sheet 40 is prepared. The decorative transfer sheet 40 is the same as the decorative transfer sheet 40 shown in Figure 6. A foamed resin layer 2 is also formed on the surface of the object to be decorated 31. Next, as shown in Figure 7(b), the decorative transfer sheet 40 and the object to be decorated 31 having a foamed resin layer 2 on its surface are placed so that the foaming suppression layer 3 surface of the decorative transfer sheet 40 and the foamed resin layer 2 surface of the object to be decorated 31 face each other and are integrated. Then, as shown in Figures 7(b) to 7(c), the release support 41 is peeled off from the decorative transfer sheet 40. As a result, the transfer layer 42 of the decorative transfer sheet 40 is transferred to the surface of the foamed resin layer 2 of the object to be decorated 31. Next, as shown in Figures 7(c) to 8, the foamed resin layer 2 is foamed to form a foamed layer 12. This results in a decorative article 30 having an uneven surface.

In areas where the foam-suppressing layer is present, the foaming of the foamable resin layer is suppressed by the foam-suppressing agent contained in the layer. Therefore, the areas with the foam-suppressing layer become concave, while areas without the foam-suppressing layer become convex. This creates an uneven surface on the decorated article.

When manufacturing a decorated article using the decorative transfer sheet described in this disclosure, the foamed resin layer and the foaming suppression layer are placed close together, thereby enhancing the foaming suppression effect.

The following describes the various components of the decorative transfer sheet in this disclosure.

1. Transfer Layer The transfer layer in this disclosure comprises, in order from the peelable support side, an image layer having a thermal transfer image and a patterned foam suppression layer.

(1) Foam suppression layer The foam suppression layer in this disclosure is molten. Because the foam suppression layer is molten, the foam suppression layer can be formed in a pattern on the surface opposite to the peelable support of the image layer by a melt-type thermal transfer method.

In this embodiment, as described above, the foam suppression layer is molten, and the foam suppression layer is formed in a pattern on the side opposite to the image layer peelable support using a molten thermal transfer method. In the molten thermal transfer method, a laminate having a peelable support and an image layer, and a molten thermal transfer sheet having a foam suppression layer are used. Thermal energy corresponding to the information of the uneven shape is applied to the molten thermal transfer sheet, and the foam suppression layer, melted or softened by the application of thermal energy, is transferred layer by layer to the image layer side of the laminate, thereby forming a pattern of foam suppression layer.

The foam-inhibiting layer contains a foam inhibitor and a molten resin.

As a foaming inhibitor, a general foaming inhibitor can be used, and it should be selected appropriately depending on the type of foaming agent and resin contained in the foamed resin layer.

In particular, to suppress the vaporization of the foam inhibitor during the thermal transfer of the foam-inhibiting layer, it is preferable that the boiling point or sublimation point of the foam inhibitor be higher than the melting start temperature of the foam-inhibiting layer. The boiling point or sublimation point of the foam inhibitor is the same as described in the section on the foam-inhibiting layer of the first embodiment of the laminate for decorative sheets described above.

The foaming inhibitor is the same as that described in the section on the foaming inhibitory layer of the first embodiment of the laminate for decorative sheets described above.

The resin contained in the foam suppression layer is not particularly limited as long as it is a molten resin; for example, a thermoplastic resin can be used. As the thermoplastic resin, a general thermoplastic resin used in the molten ink of a molten-type thermal transfer sheet can be used. The thermoplastic resin is the same as described in the section on the foam suppression layer of the first embodiment of the laminate for decorative sheets described above.

Furthermore, the foam-suppressing layer may contain wax.

Furthermore, the foam suppression layer may contain a coloring agent. In this case, the foam suppression layer and the image layer can be easily synchronized.

The foam-suppressing layer may contain additives as needed.

The method for forming the foam-suppressing layer is preferably a fusion-type thermal transfer method.

The thickness of the foam-suppressing layer is the same as that described in the section on the foam-suppressing layer of the first embodiment of the laminate for decorative sheets described above.

The foam-suppressing layer is arranged in a pattern. The pattern shape of the foam-suppressing layer in plan view is the same as that described in the section on the foam-suppressing layer in the first embodiment of the laminate for decorative sheets described above.

(2) Image layer The image layer in this disclosure has a thermal transfer image. The image layer is the same as the image layer in the laminate for decorative sheets described above.

(3) Protective layer In this disclosure, the transfer layer preferably has a protective layer 5 between the release support 41 and the image layer 4, as shown in Figure 9, for example. In a decorated article using a decorative transfer sheet, the protective layer is a member that protects the image layer and the foam layer. The protective layer can also provide scratch resistance and release properties.

The material for the protective layer is not particularly limited and includes, for example, thermoplastic resins, curable resins, etc. These materials are selected appropriately depending on the purpose.

For example, if the protective layer is made of a thermoplastic resin, it can function as a release layer, allowing for easy removal of the base layer from the decorative transfer sheet.

On the other hand, if the protective layer contains a curable resin, it becomes a hard coat precursor layer, and a hard coat layer can be obtained by curing. The hard coat layer can improve scratch resistance.

The protective layer is the same as the protective layer in the laminate for decorative sheets described above.

(4) Intermediate layer The transfer layer in this disclosure may have an intermediate layer containing an ultraviolet absorber between the image layer and the protective layer. This can improve the light resistance of the thermal transfer image on the image layer. In particular, when the protective layer is cured with ultraviolet light, degradation of the thermal transfer image due to ultraviolet light can be suppressed.

The intermediate layer is the same as the intermediate layer in the laminate for decorative sheets described above.

(5) Adhesive layer The transfer layer in this disclosure may have an adhesive layer on the side of the foam suppression layer opposite to the image layer, or between the image layer and the foam suppression layer. The adhesive layer is a component for bonding the decorative transfer sheet to an object to be decorated which has a foamable resin layer on its surface.

The adhesive layer is the same as the adhesive layer in the laminate for decorative sheets described above.

2. Peelable Support The substrate layer in this disclosure is a member that supports the image layer and the foam suppression layer. In this embodiment, after integrating the decorative transfer sheet with the object to be decorated which has a foaming resin layer on its surface, the peelable support is peeled off from the decorative transfer sheet.

The physical properties, materials, and structure of the release support are the same as those of the base layer in the laminate for decorative sheets described above.

The thickness of the release support is not particularly limited as long as it satisfies the elongation rate at 130°C as described above. For example, it may be between 30 μm and 300 μm, or between 50 μm and 125 μm. When the thickness of the release support is within this range, the handling of the decorative transfer sheet can be improved. On the other hand, if the thickness of the release support is too thick, depending on the material of the release support, it may not satisfy the elongation rate at 130°C described above.

3. Antistatic Layer The decorative transfer sheet in this disclosure may have an antistatic layer 6 on the side of the peelable support 41 opposite to the image layer 4, as shown in Figure 9, for example. The antistatic layer is a component provided to suppress the adhesion of foreign matter to the decorative transfer sheet.

For the antistatic layer, general antistatic agents can be used. Examples of such antistatic agents include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, inorganic conductive materials such as carbon and metals, and conductive polymers.

The thickness of the antistatic layer is, for example, 0.1 μm to 5 μm.

One method for forming an antistatic layer is to apply a composition containing an antistatic agent and a solvent onto a substrate layer.

4. Sublimation-preventing layer The decorative transfer sheet in this disclosure may have a sublimation-preventing layer on the side of the release support opposite to the image layer. When the decorative transfer sheet is wound into a roll, the sublimation-preventing layer can prevent the release support and the foam-suppressing layer from coming into contact. Therefore, if the foam-suppressing agent contained in the foam-suppressing layer is sublimable, the sublimation-preventing layer can suppress the decrease of the foam-suppressing agent in the foam-suppressing layer. This can suppress a decrease in the foam-suppressing effect.

Resins can be used as materials for the sublimation-preventing layer. Examples of resins include acrylic resins, polyester resins, vinyl resins, and urethane resins. These may be used individually or in combination of two or more types.

The sublimation-preventing layer may contain an antistatic agent. In this case, the sublimation-preventing layer can also function as an antistatic layer. The antistatic agent is the same as that used in the antistatic layer described above.

Furthermore, the sublimation-preventing layer may contain additives such as dyes, extenders, curing agents, catalysts, stabilizers, and initiators, as needed.

The thickness of the sublimation-preventing layer is not particularly limited, as long as it is thick enough to prevent contact between the release support and the foam-suppressing layer. For example, it may be between 1 μm and 10 μm.

One method for forming a sublimation-preventive layer is to apply a composition containing the above-mentioned resin onto a substrate layer.

5. Release Layer The decorative transfer sheet in this disclosure may have a release layer 9 between the release support 41 and the image layer 4, for example, as shown in Figure 9. The release layer can improve the peelability between the release support and the image layer. In this embodiment, after integrating the decorative transfer sheet with the object to be decorated which has a foamed resin layer on its surface, the release layer is peeled off from the decorative transfer sheet together with the release support.

The release layer is configured such that the adhesion between the release layer and the releaseable support is higher than the adhesion between the release layer and the image layer. Examples of materials for the release layer include silicone resins, fluororesins, melamine resins, and epoxy resins. Mixtures of these resins with other resins can also be used. Examples of other resins include acrylic resins, cellulose resins, and polyester resins.

The thickness of the release layer is, for example, between 0.1 μm and 1 μm.

D. Decorated Articles The decorated articles in this disclosure have two embodiments. Each embodiment will be described below.

I. Decorative Article of the First Embodiment The decorative article of this embodiment comprises, in this order, an object to be decorated, an adhesive layer, and a laminated sheet, and the laminated sheet has an uneven surface, wherein the laminated sheet comprises, in this order from the adhesive layer side, a base layer, a foamed layer, a patterned foaming suppression layer, and an image layer having a thermal transfer image, and the foaming suppression layer contains a foaming suppressant that is molten or sublimable.

Figure 10 is a schematic cross-sectional view illustrating a decorative article of this embodiment. As illustrated in Figure 10, the decorative article 30 comprises, in this order, an object to be decorated 31, an adhesive layer 32, and a laminated sheet 33, with an uneven surface on the laminated sheet 33 side. The laminated sheet 33 comprises, in order from the adhesive layer 32 side, a base layer 1, a foamed layer 12, a patterned foaming suppression layer 3, and an image layer 4 having a thermal transfer image 14. The foaming suppression layer 3 contains a foaming suppressant that is molten or sublimable.

The decorative article of this embodiment can be manufactured using the laminate for decorative sheets described above. Therefore, the decorative article of this embodiment achieves the same effects as the laminate for decorative sheets described above.

The following describes the various components of the decorative article in this embodiment.

1. Uneven Shape The decorative article of this embodiment has an uneven shape on the surface of the laminated sheet.

The cross-sectional shape of the uneven surface is not particularly limited.

Furthermore, the planar shape of the uneven surface is not particularly limited. The planar shape of the uneven surface may, for example, be linear or dotted. Examples of dotted planar shapes include circular, elliptical, triangular, and rectangular shapes.

Examples of textured patterns include wood grain grooves, stone surface irregularities, fabric surface textures, pearlescent finishes, sand textures, hairline finishes, and fine grooves, and combinations of these are also acceptable.

2. Laminated Sheet The laminated sheet in this embodiment comprises, in order from the adhesive layer side, a base layer, a foamed layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.

The base layer, foam suppression layer, and image layer are the same as those in the laminate for decorative sheets described above.

The foam layer is the same as the foam layer in the decorative sheet described above.

The laminated sheet may have an anchor layer between the base layer and the foam layer. The anchor layer is similar to the anchor layer in the laminated decorative sheet described above.

The laminated sheet may have an antistatic layer on the side of the base layer opposite to the foamed layer. The antistatic layer is the same as the antistatic layer in the laminated decorative sheet described above.

3. Adhesive layer The adhesive layer is the same as the adhesive layer in the laminate for decorative sheets described above.

The adhesive layer may be formed by providing it on a laminate for decorative sheets used in the manufacture of decorative articles, or by providing it on the object to be decorated.

4. Objects to be decorated The objects to be decorated in this disclosure are not particularly limited. Specifically, the shape, size, material, etc., of the objects to be decorated are not particularly limited.

The object to be decorated preferably has a three-dimensional shape.

Examples of materials to be decorated include fibrous materials, wood materials, resin materials, metal materials, glass materials, and ceramic materials. Examples of fibrous materials include ordinary paper, high-quality paper, and tracing paper. Examples of resins constituting resin materials include polycarbonate, acrylic resin, ABS resin (acrylonitrile-styrene-butadiene copolymer), and polyvinyl chloride. Examples of metals constituting metal materials include aluminum.

The object to be decorated may have a single-layer structure or a multi-layer structure.

5. Other Configurations The decorative article in this disclosure may have a protective layer on the side of the image layer opposite to the foam suppression layer. The protective layer is the same as the protective layer in the laminate for decorative sheets described above.

As for the method of forming the protective layer, the protective layer may be provided on a laminate for decorative sheets used in the manufacture of decorative articles, or the protective layer may be formed after the object to be decorated and the decorative sheet have been integrated.

Furthermore, the decorative article in this disclosure may have an intermediate layer between the image layer and the protective layer. The intermediate layer is the same as the intermediate layer in the laminate for decorative sheets described above.

As for the method of forming the intermediate layer, the intermediate layer may be provided in a laminate for decorative sheets used in the manufacture of decorative articles, or the intermediate layer may be formed after the object to be decorated and the decorative sheet have been integrated.

6. Method for Manufacturing Decorated Articles The decorated articles of this embodiment can be manufactured using the laminate for decorative sheets described above. The method for manufacturing the decorated articles of this embodiment may include, for example, a foaming step of foaming the foamable resin layer of the laminate for decorative sheets to obtain a decorative sheet, and an integration step of arranging the decorative sheet and the object to be decorated so that the surface of the decorative sheet facing the base layer and the object to be decorated face each other, and integrating them via an adhesive layer. Alternatively, the method for manufacturing the decorated articles of this embodiment may include, for example, an integration step of arranging the laminate for decorative sheets and the object to be decorated so that the surface of the laminate for decorative sheets facing the base layer and the object to be decorated face each other, and integrating them via an adhesive layer, and a foaming step of foaming the foamable resin layer of the laminate for decorative sheets after the integration step.

In particular, the foaming process and the integration process are preferably carried out in that order. Furthermore, in the foaming and integration processes, it is preferable to soften the base layer of the laminate for the decorative sheet by heating, while simultaneously foaming the foamable resin layer. If the object to be decorated has low heat resistance, it is difficult to perform the foaming process after the integration process. Therefore, by foaming the foamable resin layer when softening the base layer by heating, it becomes possible to use objects to be decorated that have low heat resistance.

Therefore, it is preferable that the heating temperature used to heat-foam the foamed resin layer is above the decomposition temperature of the thermal decomposition type foaming agent and above the softening point of the base layer.

The method for integrating the decorative sheet laminate or decorative sheet with the object to be decorated is not particularly limited as long as it allows for bonding of the decorative sheet laminate or decorative sheet. Examples include in-mold molding, insert molding, TOM molding, and other overlay molding methods. Overlay molding is also known as vacuum pressure forming. Among these, overlay molding is preferred. Overlay molding has advantages such as not being limited by the material of the object to be decorated.

Furthermore, if the protective layer is curable, a curing process can be performed after the integration process to cure the protective layer. Performing the curing process after the integration process can suppress cracking of the protective layer during the integration process.

The curing method for the protective layer is appropriately selected depending on the curable resin composition contained in the protective layer and includes methods such as irradiation with ionizing radiation and heating.

If the adhesive layer is curable, it can also be cured during the curing process. The curing method for the adhesive layer is appropriately selected depending on the type of adhesive, and includes methods such as irradiation with ionizing radiation, irradiation with visible light, and heating.

Furthermore, a trimming process may be performed after the integration process to trim any excess portions of the laminated material for the decorative sheet or the decorative sheet itself.

There are no particular limitations on the trimming method; for example, methods using a cutter or laser are also possible.

II. Decorated Article of the Second Embodiment The decorated article of this embodiment comprises, in this order, an object to be decorated, a foamed layer, and a laminated sheet, and the laminated sheet has an uneven surface, wherein the laminated sheet has, in order from the foamed layer side, a patterned foam suppression layer and an image layer having a thermal transfer image, and the foam suppression layer is meltable.

Figure 11 is a schematic cross-sectional view illustrating a decorative article of this embodiment. As illustrated in Figure 11, the decorative article 30 comprises, in this order, an object to be decorated 31, an adhesive layer 32, and a laminated sheet 33, with the laminated sheet 33 having an uneven surface. The laminated sheet 33 has, in order from the foamed layer 12 side, a patterned foam suppression layer 3 and an image layer 4 having a heat-transfer image 14. The foam suppression layer 3 is meltable.

The decorative article of this embodiment can be manufactured using the decorative transfer sheet described above. Therefore, the decorative article of this embodiment achieves the same effects as the decorative transfer sheet described above.

The following describes the various components of the decorative article in this embodiment.

1. Uneven Shape The decorative article of this embodiment has an uneven shape on the surface of the laminated sheet. The uneven shape is the same as the uneven shape in the decorative article of the first embodiment described above.

2. Laminated Sheet The laminated sheet in this disclosure comprises, in order from the foamed layer side, a patterned foam suppression layer and an image layer having a thermal transfer image.

The foam suppression layer and image layer are the same as those in the decorative transfer sheet described above.

The foamed layer is the same as the foamed layer in the decorated article of the first embodiment described above.

3. Objects to be decorated The objects to be decorated in this disclosure are the same as the objects to be decorated in the decorated article of the first embodiment described above.

4. Other Configurations The decorative article in this disclosure may have a protective layer on the side of the image layer opposite to the foam suppression layer. The protective layer is the same as the protective layer in the decorative transfer sheet described above.

As for the method of forming the protective layer, the protective layer may be provided on the decorative transfer sheet used in the manufacture of the decorated article, or the object to be decorated and the decorative transfer sheet may be integrated, and the protective layer may be formed after peeling off the release support.

Furthermore, the decorative article in this disclosure may have an intermediate layer between the image layer and the protective layer. The intermediate layer is the same as the intermediate layer in the decorative transfer sheet described above.

As for the method of forming the intermediate layer, the intermediate layer may be provided on a decorative transfer sheet used in the manufacture of decorated articles, or the object to be decorated and the decorative transfer sheet may be integrated, and the intermediate layer may be formed after peeling off the release support.

5. Method for Manufacturing Decorated Articles The decorated articles of this embodiment can be manufactured using the decorative transfer sheet described above. The method for manufacturing the decorated articles of this embodiment includes, for example, an integration step in which the decorative transfer sheet and the object to be decorated, which has a foamed resin layer on its surface, are placed facing each other and integrated; a peeling step in which the releaseable support is peeled off the decorative transfer sheet after the integration step; and a foaming step in which the foamed resin layer is foamed after the peeling step to form a foamed layer.

The method for integrating the decorative transfer sheet with the object to be decorated, which has a foamed resin layer on its surface, is not particularly limited and includes, for example, in-mold molding, insert molding, TOM molding, and other overlay molding methods. Among these, overlay molding is preferred. Overlay molding has advantages such as not being limited by the material of the object to be decorated.

In in-mold molding, insert molding, and overlay molding, the decorative transfer sheet is heated to soften it. In this process, to suppress the vaporization of the foam inhibitor, the heating temperature is preferably lower than the boiling point or sublimation point of the foam inhibitor.

If the protective layer is curable, a curing step may be performed after the integration step to cure the protective layer. The curing step is the same as described in the section on the decorated article of the first embodiment above.

This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure.

This disclosure provides the following [1] to [15].
[1] The substrate layer, the foamable resin layer, the patterned foam suppression layer, and the image layer having a thermal transfer image are provided in this order.
A laminate for decorative sheets, wherein the foam-suppressing layer contains a foam-suppressing agent that is molten or sublimable.
[2] The laminate for decorative sheets according to [1], having a protective layer on the side of the image layer opposite to the foam suppression layer.
[3] The laminate for decorative sheets according to [1] or [2], having an adhesive layer on the surface of the base material layer opposite to the foamed resin layer.
[4] A laminate for decorative sheets according to any one of [1] to [3], wherein the base layer has an elongation rate of 200% or more at 130°C.
[5] The substrate layer, the foam layer, the patterned foam suppression layer, and the image layer having a thermal transfer image are in this order.
The surface on the image layer side has an uneven shape,
A decorative sheet containing a foam inhibitor in which the foam-suppressing layer is molten, or in which the foam-suppressing layer is sublimable.
[6] The decorative sheet according to [5], having a protective layer on the side of the image layer opposite to the foam suppression layer.
[7] The decorative sheet according to [5] or [6], having an adhesive layer on the side of the base layer opposite to the foamed resin layer.
[8] The decorative sheet according to any one of [5] to [7], wherein the elongation rate of the base layer at 130°C is 200% or more.
[9] A decorative transfer sheet having a peelable support and a transfer layer,
The above transfer layer has, in order from the peelable support side, an image layer having a thermal transfer image and a patterned foam suppression layer.
[10] The decorative transfer sheet according to [9], wherein the transfer layer has a protective layer between the substrate layer and the image layer.
[11] The decorative transfer sheet according to [9] or [10], having an antistatic layer on the surface of the base material layer opposite to the image layer.
[12] A decorative transfer sheet according to any one of [9] to [11], wherein the base layer has an elongation rate of 200% or more at 130°C.
[13] A decorative article comprising an object to be decorated, an adhesive layer, and a laminated sheet in this order, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the adhesive layer side, a base layer, a foam layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
A decorative article containing a foam inhibitor in which the foam-suppressing layer is molten, or the foam-suppressing layer is sublimable.
[14] A decorative article comprising an object to be decorated, a foam layer, and a laminated sheet in this order, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet has, in order from the foamed layer side, a patterned foam suppression layer and an image layer having a thermal transfer image.
A decorative article having a foam-suppressing layer that is molten.
[15] The decorative article according to [13] or [14], having a protective layer on the side of the image layer opposite to the foam suppression layer.

1… Substrate layer 2… Foaming resin layer 3… Foaming suppression layer 4… Image layer 10… Laminate for decorative sheet 12… Foaming layer 14… Thermal transfer image 20… Decorative sheet 30… Decorated item 31… Object to be decorated 32… Adhesive layer 33… Laminate sheet 40… Decorative transfer sheet 41… Release support 42… Transfer layer

Claims (22)

A laminate for decorative sheets used in decorative sheets used in primary decoration or overlay molding,
It comprises, in this order, a base layer, a foaming resin layer, a patterned foaming suppression layer, and an image layer having a heat-transfer image.
A laminate for decorative sheets, wherein the foam-suppressing layer contains a foam-suppressing agent that is molten or sublimable. It comprises, in this order, a base layer, a foaming resin layer, a patterned foaming suppression layer, and an image layer having a heat-transfer image.
A laminate for decorative sheets, wherein the foam-suppressing layer contains a sublimable foam inhibitor, and the foam-suppressing layer is disposed inside the foamable resin layer. The laminate for decorative sheets according to claim 1 or 2 , wherein the image layer has a protective layer on the side opposite to the foam suppression layer. The laminate for decorative sheets according to claim 1 or 2, wherein the substrate layer has an adhesive layer on the side opposite to the foamed resin layer. The laminate for decorative sheets according to claim 1 or 2, wherein the elongation rate of the base layer at 130°C is 200% or more. A decorative sheet used for primary decoration or overlay molding,
It comprises, in this order, a base layer, a foam layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
The surface on the image layer side has an uneven shape,
A decorative sheet comprising a foam-suppressing layer having meltability, or containing a foam-suppressing agent having sublimability. It comprises, in this order, a base layer, a foam layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
The surface on the image layer side has an uneven shape,
A decorative sheet in which the foam-suppressing layer contains a sublimable foam-suppressing agent, and the foam-suppressing layer is disposed inside the foam layer. The decorative sheet according to claim 6 or 7 , wherein the image layer has a protective layer on the side opposite to the foam suppression layer. The decorative sheet according to claim 6 or 7 , wherein the base layer has an adhesive layer on the side opposite to the foamed resin layer. The decorative sheet according to claim 6 or claim 7 , wherein the elongation rate of the base layer at 130°C is 200% or more. A decorative transfer sheet having a release support and a transfer layer,
The transfer layer comprises, in order from the peelable support side, an image layer having a thermal transfer image and a patterned foam suppression layer.
A decorative transfer sheet having a foam-suppressing layer that is molten. A decorative transfer sheet according to claim 11, used for primary decoration or overlay molding. The peelable support has a sublimation prevention layer on the side opposite to the image layer,
A release layer is provided between the peelable support and the image layer,
The decorative transfer sheet according to claim 11, wherein the boiling point or sublimation point of the foaming inhibitor contained in the foaming inhibitor layer is higher than the melting start temperature of the foaming inhibitor layer. The decorative transfer sheet according to any one of claims 11 to 13, wherein the transfer layer has a protective layer between the peelable support and the image layer. A decorative transfer sheet according to any one of claims 11 to 13 , wherein the peelable support has an antistatic layer on the side opposite to the image layer. The decorative transfer sheet according to any one of claims 11 to 13 , wherein the elongation rate of the peelable support at 130°C is 200% or more. A decorative article comprising, in this order, an object to be decorated, an adhesive layer, and a laminated sheet, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the adhesive layer side, a base layer, a foamed layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
The foam-suppressing layer contains a foam-suppressing agent that is molten or sublimable ,
A decorated article, wherein the decorated article is manufactured by primary decoration or overlay molding . A decorative article comprising, in this order, an object to be decorated, an adhesive layer, and a laminated sheet, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the adhesive layer side, a base layer, a foamed layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
A decorative article wherein the foam-suppressing layer contains a sublimable foam-suppressing agent, and the foam-suppressing layer is disposed inside the foam layer. A decorative article comprising, in this order, an object to be decorated, an adhesive layer, and a laminated sheet, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the adhesive layer side, a base layer, a foamed layer, a patterned foam suppression layer, and an image layer having a thermal transfer image.
The foam-suppressing layer contains a foam-suppressing agent that is molten or sublimable,
The aforementioned image layer is a receptor layer having a thermal transfer image containing a sublimable dye,
A decorated article in which the foam-suppressing layer and the image layer overlap in a plan view. A decorative article comprising, in this order, an object to be decorated, a foam layer, and a laminated sheet, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the foamed layer side, a patterned foam suppression layer and an image layer having a thermal transfer image.
The foam suppression layer has meltability,
A decorated article, wherein the decorated article is manufactured by primary decoration or overlay molding . A decorative article comprising, in this order, an object to be decorated, a foam layer, and a laminated sheet, wherein the surface of the laminated sheet has an uneven shape,
The laminated sheet comprises, in order from the foamed layer side, a patterned foam suppression layer and an image layer having a thermal transfer image.
The foam suppression layer has meltability,
The aforementioned image layer is a receptor layer having a thermal transfer image containing a sublimable dye,
A decorated article in which the foam-suppressing layer and the image layer overlap in a plan view. The decorative article according to any one of claims 17 to 21, wherein the image layer has a protective layer on the side opposite to the foam suppression layer.