Transfer sheet and method for manufacturing decorative material using the same

Abstract

To provide a transfer sheet which easily copes with variety of demands of customers, and can impart visibility and texture of excellent matting effects, and a method for manufacturing a decorative material using the same.SOLUTION: A transfer sheet has a transfer layer on a releasable support, wherein the releasable support has a release layer on the support, the release layer is composed of a cured product of a resin composition containing 0.5 pts.mass or more and 6.0 pts.mass or less of a wrinkle formation stabilizer with respect to 100 pts.mass of a resin, a surface on the side of the transfer layer of the release layer has an uneven shape composed of irregular wrinkles, and a 60° gloss value of the release layer is 5.0 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a transfer sheet and a method for producing a decorative material using the same. [Background technology]

[0002] Conventionally, so-called decorative materials and decorative sheets have been used as articles for decorating and protecting the surfaces of, for example, interior components of buildings such as walls, ceilings, and floors, exterior components such as exterior walls, eaves ceilings, roofs, fences, and fences, fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other such building materials, general furniture such as chests of drawers, shelves, and desks, kitchen furniture such as dining tables and sinks, various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins, and surface decorative panels for cabinets and the like of home appliances and office automation equipment, interior or exterior components of vehicles, etc. With the increasing trend in customer preference for luxury goods in recent years, there has been a demand for such decorative materials, decorative sheets, and other articles with a luxurious feel.

[0003] A commonly used method for imparting a sense of luxury is to impart an uneven shape (also called an "uneven pattern") to the surface of an article to enhance the texture. Specifically, there are methods for imparting an uneven shape to the surface of an article to produce a matte effect by using "shape transfer processing using a shape transfer sheet," "embossing processing using an embossing plate or the like," "transfer method in which a transfer sheet having a layer with an uneven shape is used to transfer a layer with an uneven shape to an adherend," and the like.

[0004] For example, Patent Document 1 proposes a shaping sheet that has a layer of ionizing radiation curable resin with an uneven shape on the surface of a base sheet, and imparts a crosslinking density that prevents the uneven shape from cracking when peeled off, thereby reproducing a desired pattern shape, and a polyester decorative board that uses this shaping sheet. Furthermore, Patent Document 2 proposes a decorative sheet having a printed layer and a transparent resin layer in that order on a substrate, with an embossed pattern being applied to the outermost surface of the transparent resin layer. Furthermore, Patent Document 3 proposes a transfer sheet in which a transfer layer is provided on a base sheet, the transfer layer containing a predetermined resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2-235744 [Patent Document 2] JP 2011-073207 A [Patent Document 3] JP 2004-167828 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] As mentioned above, the trend of customers towards luxury goods is increasing, and therefore higher quality textures are being demanded. However, the uneven shape of the pattern-transfer film described in Patent Document 1 is formed by forming a predetermined pattern with a liquid-repellent resin, then applying a two-component curing resin composition containing an inorganic filler, and repelling only the two-component curing resin composition on the pattern due to the liquid-repellent effect of the liquid-repellent resin. Therefore, there is a limit to the formation of a delicate uneven shape, and it is not possible to impart an excellent matte effect, and there are cases where the desired demand cannot be met. In addition, in the case of the method of forming a concave-convex shape on the outermost surface by embossing as in Patent Document 2, the production of the embossing plate is a very time-consuming and difficult task, and a plate must be produced for each desired pattern. Therefore, it cannot be said that this method is easy to sufficiently respond to the diversity of customer demands. Furthermore, the molding process of Patent Document 1 and the embossing process of Patent Document 2 may restrict the manufacturing process, or it may be difficult to impart the uneven shape to the article depending on the material of the article to which the uneven shape is to be imparted.

[0007] The transfer sheet of Patent Document 3 can impart an uneven shape by transferring a transfer layer to an adherend. The transfer sheet of Patent Document 3 uses a base sheet kneaded with a matting agent and a base sheet subjected to sandblasting as a base sheet serving as a releasable support. The uneven shape imparted by the transfer sheet of Patent Document 3 reflects the surface shape of the base sheet serving as a releasable support. However, Patent Document 3 does not consider at all how to improve the texture by the surface shape of the base sheet serving as a releasable support. Furthermore, in order to impart a design appearance to the surface of an article such as a decorative sheet, both a concave-convex shape and a decorative layer such as a pattern layer are often added. In such cases, the inventions described in Patent Documents 1 and 3 require two different processes: a printing process for forming a pattern layer on a substrate and an embossing process for forming a concave-convex shape. This results in problems such as a long process time and high manufacturing costs.

[0008] An object of the present invention is to provide a transfer sheet that can easily meet the diverse needs of customers and that imparts excellent visibility and texture of a matte effect, and a method for producing a cosmetic material using the same. [Means for solving the problem]

[0009] In order to solve the above problems, the present invention provides the following [1] and [2]. [1] A transfer sheet having a transfer layer on a releasable support, The releasable support has a release layer on a support, The release layer is composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin, the surface of the release layer facing the transfer layer has an uneven shape composed of irregular wrinkles, and the 60° gloss value of the release layer is 5.0 or less. [2] A method for producing a decorative material, comprising the following steps (1) and (2): (1) A step of obtaining a laminate by closely adhering the transfer layer side of the transfer sheet according to any one of claims 1 to 11 to an adherend. (2) A step of peeling off the releasable support from the laminate to obtain a decorative material having a transfer layer on an adherend. Effect of the Invention

[0010] According to the present invention, it is possible to provide a transfer sheet that can easily meet the diverse needs of customers and imparts excellent visibility and texture of a matte effect, and a method for producing a decorative material using the same. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention. [Diagram 2] FIG. 2 is a plan view showing one embodiment of the surface on the release layer side of a releasable support constituting the transfer sheet of the present invention. [Diagram 3] FIG. 1 is a cross-sectional view showing one embodiment of a releasable support constituting a transfer sheet of the present invention. [Figure 4] 1 is an optical microscope image of the surface of the release layer side of the releasable support constituting the transfer sheet of Example 1. [Diagram 5] 1 is an optical microscope image of the surface of the release layer side of the releasable support constituting the transfer sheet of Example 2. [Figure 6] 1 is an optical microscope image of the surface of the release layer side of the releasable support constituting the transfer sheet of Example 3. [Figure 7] 1 is an optical microscope image of the surface of the release layer side of the releasable support constituting the transfer sheet of Comparative Example 1. [Figure 8] 1 is an optical microscope image of the surface of the release layer side of the releasable support constituting the transfer sheet of Comparative Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values ​​related to "greater than or equal to," "less than or equal to," and "to" in relation to the description of a numerical range are numerical values ​​that can be arbitrarily combined, and the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0013] [Transfer sheet] The transfer sheet of this embodiment has a transfer layer on a releasable support, and the releasable support has a release layer on the support, and the release layer is composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin, and the surface of the release layer facing the transfer layer has an uneven shape composed of irregular wrinkles, and the 60° gloss value of the release layer is 5.0 or less.

[0014] Fig. 1 is a cross-sectional view showing one embodiment of the transfer sheet of the present invention. The transfer sheet 100 in Fig. 1 has a transfer layer 20 on a releasable support 10. Also, in Fig. 1, the releasable support 10 has a release layer 12 on a support 11. Also, in Fig. 1, the transfer layer 20 has, from the side closer to the releasable support 10, a peeling layer 21, a primer layer 22, a decorative layer 23, and an adhesive layer 24 in this order.

[0015] <Releasable support> The releasable support in the transfer sheet of the present embodiment has a release layer on the support, and is peeled off from the transfer layer after the transfer layer is transferred to the adherend.

[0016] [Support] The form (or shape) of the support is not particularly limited, but considering the use as a transfer sheet, it is preferable that the support has a planar shape such as a film, sheet, plate, etc. Here, the film, sheet, and plate are usually called film, sheet, and plate in order of their relatively thinness, but in this specification, there is no particular significance in strictly distinguishing between these three, and the difference between film, sheet, and plate does not cause any difference in the interpretation of the rights of the present invention. Therefore, the "sheet" in "transfer sheet" includes not only what is generally called a sheet, but also what is generally called a film or plate-like shape. In addition, in this specification, the films, sheets, and plates may be collectively referred to as "sheets", "sheet-like", etc. When the support is a sheet, as described above, it is easy to use as a transfer sheet, and it is also easy to form a release layer on the support, as well as transfer layers such as a peeling layer, primer layer, decorative layer, and adhesive layer, thereby improving manufacturing suitability.

[0017] As the support, any support (substrate) that is normally used for articles such as decorative materials and decorative sheets can be used without any restrictions, and representative examples include supports (substrates) made of fibrous materials such as paper, nonwoven fabric and woven fabric, resin, metal, etc., and supports made of fibrous materials and resin are preferred. Among these, resin supports are preferred because they are easy to form a release layer on and have good peeling workability after transfer. Hereinafter, supports made of resin are also referred to as plastic sheets. The support may be a single layer, or may be a laminate of two or more layers made of the above materials. When the support is a laminate of two or more layers, it is preferable that the two or more layers are made of different materials, and the properties of the materials of each layer are mutually complemented.

[0018] When a multi-layer support is used, each layer constituting the multi-layer structure, for example, a laminate formed by laminating a layer composed of material A and a layer composed of material B, is expressed as "A / B"; (1)Resin / metal materials (2) Resin / fibrous materials (3) Resin 1 / Resin 2 (for example, when there are multiple layers made of different resins such as "olefin resin / acrylic resin") The following embodiments are preferred. Furthermore, when the support has multiple layers, it may further have an adhesive layer, a pressure-sensitive adhesive layer, or a primer layer (also called an anchor layer or an easy-adhesion layer) between each of the multiple layers as a layer for improving the adhesion between adjacent layers.

[0019] Examples of fibrous material supports include paper supports such as kraft paper, titanium paper, linter paper, parchment paper, wallpaper backing paper, tissue paper, wood-free paper, Japanese paper, paperboard, and gypsum board base paper. Paper supports may further contain various resins such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin (impregnated with resin after papermaking, or filled in during papermaking) in order to improve the interlaminar strength between the fibers or between the paper supports of multiple layers, and to prevent fuzzing. Examples of such paper supports include inter-paper reinforced paper and resin-impregnated paper. Examples of supports in which a resin layer is laminated on a fibrous material layer include wallpaper rolls in which various resin layers such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer are laminated on the surface of wallpaper backing paper, which is commonly used in the field of building materials.

[0020] Examples of nonwoven or woven fabric supports include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon; organic fibers made of various synthetic resins such as polyester resin, acrylic resin, polyethylene, and polypropylene; protein-based or cellulose-based natural fibers such as silk, cotton, and hemp; nonwoven or woven fabrics made of various fibers such as glass fiber and carbon fiber; and composites of these.

[0021] Examples of the resin support include substrates made of various resins such as synthetic resins, natural resins, etc. As the synthetic resin, a thermoplastic resin or a curable resin can be used. Examples of thermoplastic resins include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin-based thermoplastic elastomers, and ionomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; polymethyl (meth)acrylate, polybutyl (meth)acrylate, and the like. Examples of resin supports include acrylic resins such as methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane, and celluloid; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene resins (ABS resins); and thermoplastic resins such as polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins. Examples of the curable resin include the ionizing radiation curable resin capable of forming the matte layer described above, and other thermosetting resins. Examples of natural resins include natural rubber, rosin, and amber.

[0022] Examples of the metallic support include aluminum or various aluminum alloys, iron or various iron alloys such as carbon steel, tin, copper, nickel, etc. The metallic support may be in the form of a film or sheet having a thickness of about 10 μm to 100 μm, which is called a metal foil.

[0023] The support may be colored or uncolored. In addition, when the support is colored, the mode of coloring is not particularly limited, and the support may be transparently colored or opaquely colored (hiding colored).

[0024] The support may contain additives as necessary. In the case of a resin, examples of additives include inorganic substances such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of additives to be added is not particularly limited as long as it does not impair surface properties, processing properties, and the like, and can be appropriately set according to the required properties, etc.

[0025] From the viewpoint of preventing deterioration of the transfer sheet of the present embodiment, among the above additives, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers. Examples of the ultraviolet absorbers and light stabilizers include those exemplified as those that can be contained in the release layer described later. These ultraviolet absorbents, weather resistance agents such as light stabilizers, and other various additives may be used alone or in combination of two or more kinds.

[0026] There is no particular limitation on the thickness of the support. That is, the support in this embodiment may be a support having a thin thickness in the order of micrometers, or a support having a thick thickness in the order of millimeters or more.

[0027] When a plastic sheet is used as the support, its thickness is not particularly limited, but in order to improve the handleability of the transfer sheet, it is preferably from 10 μm to 200 μm, more preferably from 15 μm to 150 μm, and even more preferably from 20 μm to 125 μm.

[0028] In order to increase adhesion to the release layer, the support may be subjected to a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, or an easy-adhesive layer may be formed on one or both sides of the support. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferred from the viewpoints of the effect of the surface treatment and operability, etc.

[0029] [Release layer] The release layer in the transfer sheet of this embodiment is a layer formed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass to 6.0 parts by mass to 100 parts by mass of resin (hereinafter, sometimes referred to as a "resin composition for forming a release layer.") That is, in this embodiment, the release layer is a layer containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass to 6.0 parts by mass to 100 parts by mass of resin forming the release layer.

[0030] (Wrinkle formation stabilizer) The wrinkle formation stabilizer stabilizes the formation of wrinkles on the surface of the release layer, thereby achieving uniform visibility of the matte effect over the entire surface of the release layer of this embodiment and reducing partial unevenness in gloss, thereby imparting texture as well as stable visibility of the matte effect (hereinafter, the term "stable visibility of the matte effect" or similar expressions may be used). The above-mentioned "stabilization of wrinkle formation" of the wrinkle formation stabilizer means, more specifically, that the shape of the "wrinkles" and their geometric characteristic values ​​(the length, width and ratio of each protrusion (convex portion) in the uneven shape of the wrinkles, as well as various numerical values ​​and indexes such as Rz (maximum height), Rsm (average length of curved elements), Ra (arithmetic mean roughness), Ssk (skewness), Sku (kurtosis), and the like, as well as the in-plane distribution (variance σ), etc., converge when the "wrinkle formation stabilizer" is used compared to when the "wrinkle formation stabilizer" is not used.

[0031] In the transfer sheet of this embodiment, the surface shape of the transfer layer reflects the surface shape of the releasable support (≒ surface shape of the release layer). Therefore, since the release layer of the transfer sheet of this embodiment has a matte effect and texture, the decorative material obtained by transferring the transfer layer of the transfer sheet has a matte effect and texture (which can be collectively called "luxury feel"). In other words, even if the so-called "matte agent" in the prior art and the "wrinkle formation stabilizer" in this embodiment have the same constituent substances and average particle diameter, they are different in the matte mechanism (action), the structure for expressing the matte effect, and the relationship between the amount used and the degree of surface gloss (gloss value).

[0032] In the prior art, the matte agent used for matte expression exerts a matte effect by itself due to the light diffusion effect caused by the physical shape. Specifically, what is generally called a matte agent generally has a refractive index difference between the matte agent particle and the surrounding resin and air, and the shape corresponding to the outline shape of the particle exerts the visibility of the matte effect by the light diffusion effect due to the reflection and refraction interface of light rays. On the other hand, in the transfer sheet of the present embodiment, the wrinkle formation stabilizer does not exert the visibility of the matte effect by the light diffusion due to the reflection and refraction of light rays by the particle itself, but stabilizes the formation of wrinkles on the surface of the release layer due to the wrinkle formation stabilizer at the refractive index difference interface between the surface and air, and imparts a texture to the transfer sheet together with the visibility of the matte effect stably due to the light diffusion effect caused by the shape of the wrinkles. Therefore, the wrinkle formation stabilizer used in this embodiment is different from a matting agent that itself exhibits a visible matting effect in terms of the matting mechanism (action) and structure for exhibiting the matting effect (even if the constituent substances and average particle diameters of the two are the same). Furthermore, the relationship between the content and the surface gloss (gloss value) of the "wrinkle formation stabilizer" and the "matt agent" is also different. When the same substance A is used as a wrinkle formation initiator AW (W: an abbreviation for wrinkles) and a specific amount C is added to form wrinkles on the surface, the 60° gloss value G of the surface is 60° AW(C) is the 60° gloss value G of the surface when the substance A is used simply as a matting agent AM (M: an abbreviation of matte) and is added in the specific amount C, but no wrinkles are formed on the surface. 60° AM (C) is clearly lower than that of (C). In other words, the following relationship holds: G 60° AW (C) <G 60° AM (C)

[0033] The release layer may contain an agent that has been used as a matting agent in the past, but it is preferable that it does not contain a matting agent. Thus, it can be said that the transfer sheet of the present embodiment has extremely excellent visibility and texture of the matting effect even if it does not substantially contain a matting agent that has been used in the past to obtain visibility of the matting effect. Therefore, when a matting agent is contained (added), it is sufficient to reinforce the matting effect due to wrinkles on the surface of the release layer. Here, "not containing a matting agent" means that in addition to not containing a matting agent at all, even if it is contained, there is no visibility of the matting effect based on the action and effect of the matting agent itself, specifically, the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the resin. In this specification, the term "matte agent" refers to particles having an average particle diameter whose lower limit is the smaller of more than 100% of the thickness of the layer in which the matte agent can be contained, i.e., the release layer, and more than 30 μm, from the viewpoint of forming convex portions by the head exposure effect as described above.

[0034] The wrinkle formation stabilizer is not a matte agent as described above, and has an average particle size of 100% or less of the thickness of the release layer, and various particles such as organic particles, inorganic particles, etc. can be used. In this embodiment, if a wrinkle formation stabilizer is not used, the formation of wrinkles becomes unstable, and the visibility and texture of the excellent matte effect due to the formation of wrinkles cannot be stably obtained as a whole.

[0035] The wrinkle formation stabilizer used in this embodiment can be any particle that is not a matte agent and has an average particle size preferably of 100% or less of the thickness of the release layer or 30 μm or less, whichever is smaller, and is preferably used as the wrinkle formation stabilizer 1 having an average particle size of 1 μm or more and an upper limit of 100% or less of the thickness of the release layer or 30 μm or less, whichever is smaller, and as the wrinkle formation stabilizer 2 having an average particle size of less than 1 μm. In this embodiment, as the wrinkle formation stabilizer, one or more types of wrinkle formation stabilizer 1 may be used, one or more types of wrinkle formation stabilizer 2 may be used, or one or more types of wrinkle formation stabilizer 1 and one or more types of wrinkle formation stabilizer 2 may be used in combination. In this embodiment, it is preferable to use two types of wrinkle formation stabilizers, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect.

[0036] As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of organic substances that constitute the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, and polyester-based resin. Examples of inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate. Among these, silica, which has excellent transparency, is preferred.

[0037] The shape of the wrinkle formation stabilizer is not particularly limited, but examples thereof include spherical, polyhedral, scaly, and amorphous shapes.

[0038] From the viewpoint of stabilizing the formation of wrinkles and improving the visibility and texture of the matte effect, the average particle diameter of the wrinkle formation stabilizer is preferably 90% or less of the thickness of the release layer, more preferably 80% or less of the thickness of the release layer, and even more preferably 70% or less of the thickness of the release layer, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less, and the upper limit of the thickness of the release layer and the upper limit of the absolute value may be the smaller of any combination. For example, the upper limit may be the smaller of 90% or less of the thickness of the release layer and 20 μm or less, or the smaller of 90% or less of the thickness of the release layer and 10 μm or less. The thickness of the release layer will be described later. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more.

[0039] When wrinkle formation stabilizers 1 and 2 are used separately as described above, the average particle diameter of wrinkle formation stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.8 μm or more, from the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, with the upper limit being as described above. From a similar viewpoint, the average particle diameter of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more, with the upper limit being preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less. In this specification, the average particle size of the wrinkle formation stabilizer is measured as the mass average value d50 in particle size distribution measurement by a laser light diffraction method.

[0040] The content of the wrinkle formation stabilizer is 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the resin forming the release layer. If it is less than 0.5 parts by mass, the effect of using the wrinkle formation stabilizer cannot be obtained, and the formation of wrinkles is not stable, so the visibility and texture of the matte effect cannot be obtained stably. On the other hand, even if it exceeds 6.0 parts by mass, the formation of wrinkles becomes difficult to stabilize, and the visibility and texture of the matte effect cannot be obtained stably. When wrinkle formation stabilizers 1 and 2 are used in combination as the wrinkle formation stabilizer, the above content means the total content of these.

[0041] In order to stabilize the formation of wrinkles by the wrinkle formation stabilizer and stably improve the visibility and texture of the matte effect, the total content of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 is preferably 0.75 parts by mass or more, more preferably 1.0 part by mass or more, and even more preferably 1.2 parts by mass or more, relative to 100 parts by mass of the resin forming the release layer, and there is no particular upper limit as long as it is 6.0 parts by mass or less from the viewpoint of improving the visibility of the matte effect.

[0042] The content of each of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 is not particularly limited as long as the total content is within the above range, but the content of the wrinkle formation stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, and the upper limit is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.5 parts by mass or less, relative to 100 parts by mass of the resin. The blending ratio of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 (wrinkle formation stabilizer 1 / wrinkle formation stabilizer 2) is preferably 0.05 to 0.95, more preferably 0.10 to 0.90, even more preferably 0.20 to 0.80, and even more preferably 0.30 to 0.70.

[0043] (Surface shape of release layer) The release layer is a layer composed of a cured product of a resin composition for forming a release layer containing the above-mentioned specific wrinkle formation stabilizer at a specific content, and as described above, the wrinkle formation is stabilized on the surface of the release layer, and the layer stably expresses the visibility and texture of the matte effect due to the light diffusion effect caused by the shape of the wrinkles. The surface shape of the release layer is reflected in the surface shape of the transfer layer. Therefore, the surface shape of the release layer is reflected as the surface shape of the decorative material obtained by transferring the transfer layer to the adherend. Therefore, the matte effect and texture of the release layer are reflected in the matte effect and texture of the decorative material obtained by transferring the transfer layer to the adherend.

[0044] Fig. 2 is a plan view showing one embodiment of the surface on the release layer side of the releasable support constituting the transfer sheet of this embodiment. Fig. 2 is also a schematic image of the surface on the transfer layer side of the releasable support obtained in the examples. Fig. 2 shows that wrinkles are formed on the surface of the releasable support of this embodiment (the surface of the release layer of this embodiment).

[0045] The uneven shape formed by the wrinkles appearing on at least one surface of the release layer is stabilized by the wrinkle formation stabilizer, and the visibility and texture of the matte effect are stably expressed. In addition, it is preferable that the irregular wrinkles are formed by a plurality of convex parts formed by a plurality of protrusions and a concave part formed by being surrounded by the plurality of protrusions, and it is preferable that the protrusions have linear protrusions. In this specification, "linear protrusions" (hereinafter also referred to as "linear protrusions") means that the ratio of the length to the width of the protrusions (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more, and the method of determining the length and width is as described below. In this embodiment, more preferable irregular wrinkles are those constituted by a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.

[0046] An example of the wrinkles is shown in Fig. 2. Fig. 2 shows that the surface of the release support, i.e., the surface of the release layer, has irregular wrinkles in plan view, and that the irregular wrinkles are formed by including a plurality of convex portions 3 formed by a plurality of curved linear protrusions and a concave portion 2 formed by being surrounded by a plurality of protrusions (a plurality of convex portions 3), and that at least a portion of the curved plurality of convex portions 3 is formed by a meandering linear protrusion, and that the meandering concave portion 2 is formed so as to be surrounded by the meandering linear protrusion. The transfer sheet of this embodiment stably exhibits the visibility and texture of the matte effect due to the stable formation of the wrinkles shown in Fig. 2.

[0047] Here, "curved" means that there is one or more portions where the extension direction of the continuous linear protrusions 3 is reversed from one side to the other side in plan view. Examples of portions where the extension direction is reversed from one side to the other side include a form having an inflection point when the linear protrusions 3 are approximated by a continuous curve when the width of the plan view shape is ignored (when the width is considered to be 0). Also, examples include a form having a portion that is approximated by a V-shaped folded line or two sides sandwiching one vertex of a triangle when the linear protrusions 3 are approximated by a straight line when the width of the plan view shape is ignored. Moreover, "meandering" means that there are at least two or more portions where the extension direction of the continuous linear protrusions 3 is reversed from one side to the other side in a plan view (hereinafter also referred to as "reversed portions"), and when proceeding in the extension direction of the linear protrusions 3, there are portions where the extension direction of the linear protrusions 3 is reversed alternately in two adjacent portions. For example, when the width of the plan view shape of the linear protrusions 3 is ignored and approximated by a continuous curve, an example of such a shape is one having a portion that is approximated by the Roman letter "S". When the width of the plan view shape of the linear protrusions 3 is ignored and approximated by a straight line, an example of such a shape is one having a portion that is approximated by the Roman letter "W".

[0048] In this specification, irregular means that the shape does not have a certain rule, and the shape is not arranged according to a certain rule, i.e., it is not patterned. A typical example of a shape that is not irregular (regular shape) is a shape arranged with a certain periodicity in a specific direction, such as a so-called "lenticular lens" in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to the longitudinal direction. Therefore, the irregular wrinkles in this embodiment include the shape of a single protrusion itself being irregular, not formed according to a certain rule such as periodicity, the shape of a plurality of convex parts formed by a plurality of protrusion parts being irregular, not formed and arranged according to a certain rule, and the shape of a concave part surrounded by such a plurality of protrusion parts being irregular. In the release layer constituting the transfer sheet of this embodiment, if any of the shape of one protrusion (one convex portion), the shape and arrangement of each of the multiple protrusions (multiple convex portions), and the shape of the concave portion surrounded by the multiple protrusions is irregular, the visibility and texture of the matte effect due to the irregular wrinkles can be obtained, but it is preferable that all of them are irregular. In the transfer sheet of this embodiment, the visibility and texture of the matte effect are improved by the release layer having irregular wrinkles, and the extremely excellent visibility and texture of the matte effect are stably expressed.

[0049] As described above, the release layer has wrinkles, i.e., an uneven shape, on at least one surface thereof. The convex and concave portions in the uneven shape may be classified by binarization processing, for example, using the brightness difference of the image on the surface of the transfer sheet of this embodiment, with the darkest part of the concentration distribution image being set to gradation 255 and the lightest part of the concentration distribution image being set to gradation 0, with gradations 0 to 255 being set to gradations 0 to 127 as concave portions and gradations 128 to 255 as convex portions.

[0050] The surface of the release layer constituting the transfer sheet of this embodiment is preferably formed with irregular wrinkles at least in a part thereof, and more preferably formed with irregular wrinkles over the entire surface. The location where the wrinkles are formed is not particularly limited as long as it is the surface of the release layer, and is not limited to, for example, only the location corresponding to the decorative layer described later, but as long as it is at least a part of the surface of the release layer, the visibility and texture of the matte effect due to the formation of the wrinkles are expressed. As shown in Fig. 2, the surface of the release layer preferably has a plurality of convex portions formed by a plurality of protrusions having a certain degree of uniformity, even though they are irregular, and a concave portion surrounded by the convex portions. Therefore, a shape in which the width or height of one convex portion (protrusion portion) changes drastically is not a preferable embodiment for obtaining the visibility and texture of the matte effect. Specific embodiments of the shapes of the convex portions (protrusion portions) and concave portions that form irregular wrinkles and that can be advantageous in stably improving the visibility and texture of the matte effect will be described below.

[0051] Regarding the shape of the wrinkles formed on at least one surface of the release layer, the height of the convex portion (height of the protrusion portion) is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with the upper limit being about 10 μm or less. The width of the convex portion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, with the upper limit being preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. When the height and width of the convex portion are within the above range, the visibility and texture of the matte effect are stably improved in relation to the concave portion. Here, the above dimensions of the convex portion are the average values ​​of any 10 convex portions (projections) at any 10 locations (100 μm square area × 10 locations) of the release layer constituting the transfer sheet of this embodiment, that is, a total of 100 convex portions. Also, as shown in FIG. 2, the width of one convex portion (projection) is not the same but varies between wide and narrow, so the width of one convex portion (projection) is the average value of the widths at any 5 locations of that one convex portion (projection). The same applies to the height of the convex portion (projection).

[0052] The depth of the recess is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with the upper limit being about 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, with the upper limit being preferably 10 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. When the depth and width of the recess are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the protrusions. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0053] The distance from the top of the convex portion to the bottom of the concave portion (height difference between the convex portion and the concave portion) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. When the distance is within the above range, the visibility and texture of the matte effect are stably improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0054] The proportion of the projections is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. When the proportion of the projections is within the above range, the visibility and texture of the matte effect are stably improved in relation to the proportion of the recesses surrounded by the projections. Here, the occupancy rate of the convex portions is the average value of the occupancy rate of the convex portions at any 10 locations (100 μm square area×10 locations) on the release layer constituting the transfer sheet of this embodiment.

[0055] The convex portions and concave portions may have portions of approximately the same direction and width, but from the viewpoint of stably improving the visibility and texture of the matte effect, it is preferable that the length is short. Specifically, the length of the convex portions and concave portions of approximately the same direction and width continuing is preferably 95 μm or less, more preferably 80 μm or less, even more preferably 70 μm or less, and the lower limit is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, so that the visibility and texture of the matte effect are stably improved. Here, of any 10 convexities and concaves (i.e., a total of 100 convexities and concaves) in any 10 locations (100 μm square area × 10 locations) of the release layer constituting the transfer sheet of this embodiment, it is preferable that 80% or more of them satisfy the above conditions, more preferably 85% or more, even more preferably 90% or more, and even more preferably 95% or more. In addition, in this specification, "almost the same" means that it is roughly the same, without branching, and means that the difference in direction is within ±3°, and the difference in width is within ±5%.

[0056] The number of convex portions (projections) in a 100 μm square region is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. When the number of the convex portions is within the above range, the visibility and texture of the matte effect are stably improved. The number of convex portions is the average number of convex portions at 10 locations (100 μm square area×10 locations) on the release layer constituting the transfer sheet of this embodiment.

[0057] FIG. 3 is a cross-sectional view showing one embodiment of a releasable support 10 constituting the transfer sheet of the present embodiment, the cross-sectional view being taken along a plane parallel to the thickness direction (the Z direction in the figure) of the releasable support. The shape of the recess may be, for example, an acute angle as shown in 2a in Fig. 3, a semicircular or semielliptical shape as shown in 2b, or a combination of these.Furthermore, a shape such as 2c in Fig. 3, in which one protrusion has a recess in a part, may be used. On the other hand, the shape of the convex portion is semicircular or semielliptical, although the width varies as shown in 3a and 3b in FIG.

[0058] The thickness of the release layer is not particularly limited as long as it is a thickness that can form the above-mentioned wrinkles to a degree that can stably express the visibility and texture of the matte effect, but taking into consideration ease of production, etc., the thickness is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and even more preferably 5 μm or more, with the upper limit being preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and even more preferably 100 μm or less. In this specification, the thickness of the release layer is the average value of the thicknesses of 20 points measured from an image of the cross section of the transfer sheet taken with a scanning electron microscope (SEM). The acceleration voltage of the SEM is set to 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[0059] From the viewpoint of improving the visibility and texture of the stable matte effect, the release layer is preferably provided over the entire surface of the support. When the release layer is provided partially on the support, the surface shape of the transfer layer transferred to the adherend will have a shape that does not partially reflect the surface shape of the release layer. When the release layer is provided partially on the support, it is preferable to have a second release layer on the part of the support that does not have a release layer. The shape and composition of the second release layer are not particularly limited as long as it has releasability and does not inhibit the effects of the present invention.

[0060] (resin) The resin for forming the release layer may be any resin that is a resin that forms a release layer by forming a resin composition for forming the release layer containing a predetermined amount of the above-mentioned wrinkle formation stabilizer and curing it to become a cured product that constitutes the release layer. Examples of such resins include ionizing radiation curable resins.

[0061] The ionizing radiation curable resin is a resin having an ionizing radiation curable functional group, and the ionizing radiation curable functional group is a group that crosslinks and cures by irradiation with ionizing radiation, and preferable examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. In this specification, the (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In addition, in this specification, the (meth)acrylate refers to an acrylate or a methacrylate. In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet rays (UV) or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0062] Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet ray curable resins. From the viewpoint of stabilizing the formation of wrinkles caused by the wrinkle formation stabilizer and improving the visibility and texture of the matte effect, ultraviolet ray curable resins are preferred. Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0063] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Here, "(meth)acrylate" means "acrylate or methacrylate". The polyfunctional (meth)acrylate monomer includes a (meth)acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group.

[0064] From the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further improving surface properties such as scratch resistance and weather resistance, and processing properties, the number of functional groups in the polyfunctional (meth)acrylate monomer is preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 2 to 4, and even more preferably from 2 to 3. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0065] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. Further examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chains, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecules of novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc.

[0066] These polymerizable oligomers may be used alone or in combination of two or more kinds. From the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further from the viewpoint of improving surface properties such as scratch resistance and weather resistance, and processing properties, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

[0067] The number of functional groups of these polymerizable oligomers is preferably from 2 to 8 in terms of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further from the viewpoint of improving surface properties such as scratch resistance and weather resistance, as well as processing properties, and the upper limit is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. From the same viewpoint, the weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and even more preferably from 3,500 to 6,000. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0068] In this embodiment, the resin forming the release layer is preferably a combination of the above-mentioned polymerizable oligomer and polymerizable monomer.In this case, the content of the polymerizable oligomer relative to the total 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more, and the upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 70 parts by mass or less.When the content of the polymerizable oligomer is within the above range, it can stabilize the formation of wrinkles, stably improve the visibility and texture of the matte effect, and further improve the surface properties such as scratch resistance and weather resistance, and processing properties.

[0069] (Resin composition) The release layer is composed of a cured resin composition containing the above-mentioned wrinkle formation stabilizer in a predetermined content, and the resin composition specifically contains the above-mentioned resin and the above-mentioned wrinkle formation stabilizer in a predetermined content. The resin composition used in this embodiment may contain other components in addition to the above-mentioned wrinkle formation stabilizer and resin, depending on the desired performance, etc. The resin composition for forming the release layer may contain a monofunctional (meth)acrylate, for example, for the purpose of reducing the viscosity of the composition. These monofunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0070] In addition, when the resin is an ultraviolet-curable resin that is cured by ultraviolet light, it is preferable to contain additives such as a photopolymerization initiator, a photopolymerization accelerator, etc. By containing these additives, the formation of wrinkles is promoted, and the visibility and texture of the matte effect are improved. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing speed, and examples of the accelerator include one or more types selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0071] In addition, the release layer preferably has good releasability from the transfer layer. For this reason, the release layer preferably contains a release agent. Examples of the release agent include a fluorine-based release agent and a silicone-based release agent, and the silicone-based release agent is preferable from the viewpoint of obtaining a lower cost and higher releasability.

[0072] Examples of silicone-based release agents include those having a polysiloxane structure as a basic structure, and among them, modified silicone oils having an organic group introduced at least in one of the side chain and the terminal are preferred, and modified silicone oils having an organic group introduced at both terminals are more preferred. From the viewpoint of obtaining a design with a higher texture, preferred examples of the organic group include reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenol groups, and carboxyl groups, and non-reactive functional groups such as polyether groups, aralkyl groups, fluoroalkyl groups, alkyl groups, fatty acid amide groups, and phenyl groups. Among them, reactive functional groups are preferred, and (meth)acrylic groups are particularly preferred, that is, (meth)acrylic modified silicone oils are particularly preferred. In addition, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

[0073] The content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 1 to 2 parts by mass, based on 100 parts by mass of the resin forming the release layer. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.

[0074] [60° gloss value] In the transfer sheet of this embodiment, the release layer has an uneven shape formed by the above-mentioned irregular wrinkles, and the 60° gloss value of the release layer is 5.0 or less, so that a transfer layer having excellent visibility and texture of the matte effect can be formed on the adherend. In this specification, "matte" means that the gloss is difficult to be visually recognized, and although it cannot be generalized because it varies depending on the color tone of the transfer layer, for example, a 60° gloss value of 5.0 or less is treated as "matte". In addition, the transfer sheet of this embodiment imparts matte by the release layer, and can impart the above-mentioned uneven shape and 60° gloss value of the release layer. Therefore, the 60° gloss value of the release layer means the 60° gloss value that can be imparted by the transfer sheet of this embodiment (the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend).

[0075] If the release layer constituting the transfer sheet of this embodiment has a stable matte effect and texture due to stable wrinkle formation, the decorative material obtained by transferring the transfer layer to an adherend can also be a luxurious decorative material having stable visibility of the matte effect and texture. The 60° gloss value of the releasable support (release layer) constituting the transfer sheet and the 60° gloss value of the decorative material obtained by transferring the transfer layer to an adherend will be basically the same if the color tones of the two are similar, although there will be some differences.

[0076] Until now, for example, in the case of a decorative material that has a dark color such as black, it has been possible to impart excellent visibility with a 60° gloss value of 5.0 or less, even if a transfer sheet containing a matte agent is used in the release layer. "Dark color" means a color with low brightness, for example, a color with a low CIE (International Commission on Illumination) L value measured in accordance with JIS Z8781-4:2013. * a * b * L in color space * value (hereinafter simply referred to as "L *This is sometimes referred to as the "60° gloss value." This means that the 60° gloss value is usually about 40 or less, preferably 30 or less. However, since a large amount of matte agent is used, streaks and unevenness occur when the release layer is formed, making it difficult to manufacture, and there is also the problem of reduced strength of the release layer. In addition, for decorative materials that exhibit color tones other than dark colors, it is difficult to reduce the 60° gloss value to a level that is called matte, and even if a transfer sheet containing a matte agent is used in the release layer, there is a limit to how much the 60° gloss value can be reduced. This tendency becomes more pronounced as the 60° gloss value is reduced. Therefore, in the conventional technology using a matting agent, it is necessary to reduce the amount of the matting agent used for manufacturing reasons, etc., and therefore it has not been possible to obtain a more excellent matting effect in terms of visibility.

[0077] In the transfer sheet of the present embodiment, the wrinkle formation stabilizer is used and the content is small as described above, so that the formation of wrinkles is stabilized, and a stable excellent matte effect and texture can be obtained. In addition, by limiting the amount of the wrinkle formation stabilizer to an extremely small amount, a significant increase in the viscosity of the resin composition can be suppressed, which improves the productivity of the release layer.

[0078] The transfer sheet of this embodiment cannot be generally defined because it varies depending on the color tone as described above, but it can exhibit an extremely excellent visibility of the matte effect with a 60° gloss value of 5.0 or less on the release layer side of the releasable support. Also, as described above, the 60° gloss value of the release layer side of the releasable support constituting the transfer sheet of this embodiment is substantially the same as the 60° gloss value of the surface of the decorative material obtained by transferring the transfer layer to the adherend. In this specification, the 60° gloss value refers to the 60° specular gloss measured in accordance with JIS K 5600-4-7:1999, and is the average value of values ​​that can be measured at any 10 points using a gloss meter or the like. When measuring the 60° gloss value, it is preferable to attach a black plate to the back of the measurement sample via an adhesive layer in order to suppress reflection from the back of the sample.

[0079] [Other layers] The releasable support constituting the transfer sheet of the present embodiment may have layers other than the support and the release layer. Examples of the layers other than the support and the release layer include an antistatic layer and an easy-adhesion layer.

[0080] <Transfer layer> The transfer layer is a layer that is transferred to an adherend. The transfer layer preferably has at least a release layer. The transfer layer more preferably has a release layer and an adhesive layer in this order from the releasable support side. The transfer layer more preferably has one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. When a primer layer and a decorative layer are present between the release layer and the adhesive layer, it is preferable that the primer layer is located closer to the release layer than the decorative layer.

[0081] The transfer layer may further include other functional layers, such as an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an antifogging layer, and a transparent conductive layer.

[0082] [Release layer] The release layer is a layer located on the outermost surface of the transfer layer when it is transferred to an adherend, and therefore it is preferable that the release layer has good scratch resistance, weather resistance, stain resistance, etc.

[0083] The release layer preferably contains a resin as a main component, which means that the main component is 50% by mass or more of the total solid content constituting the release layer, preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0084] In order to improve scratch resistance, the release layer preferably contains, as the resin, a cured product of a resin composition containing a curable resin. The proportion of the cured product of the resin composition containing a curable resin relative to the total amount of resin contained in the release layer is preferably 50 mass% or more, more preferably 70 mass% or more, more preferably 90 mass% or more, more preferably 95 mass% or more, and more preferably 100 mass%.

[0085] Examples of the cured product of the resin composition containing a curable resin include a cured product of a resin composition containing a thermosetting resin and a cured product of a resin composition containing an ionizing radiation curable resin. A cured product of a resin composition containing a thermosetting resin is preferred in that there is no restriction on the use of an ultraviolet absorbing agent and therefore it is easy to achieve good weather resistance. A cured product of a resin composition containing an ionizing radiation curable resin is preferred because it is easy to improve scratch resistance. Among them, a cured product of a resin composition containing an electron beam curable resin is preferred because it is easy to improve weather resistance while improving scratch resistance and has no restrictions on the use of ultraviolet absorbers.

[0086] The resin composition containing a thermosetting resin is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, urethane acrylic resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. These can be used alone or in combination of two or more kinds. In addition, the resin composition containing a thermosetting resin may be one to which a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent is added.

[0087] The resin composition containing an ionizing radiation curable resin for the release layer may be any of those exemplified as the resin composition containing an ionizing radiation curable resin for the release layer, and a urethane acrylic resin such as a urethane (meth)acrylate oligomer is preferred.

[0088] The release layer may contain particles such as a matting agent and a wrinkle formation stabilizer, but it is preferable that the release layer does not substantially contain the particles. By substantially not containing particles in the release layer, it is possible to suppress a decrease in the scratch resistance, weather resistance, stain resistance, etc. of the release layer caused by the falling off of particles. When the release layer is substantially free of particles, it means that the particle content is 1% by mass or less of the total solid content constituting the release layer, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and more preferably 0% by mass.

[0089] As described above, the release layer becomes the layer located on the outermost surface of the transfer layer when transferred to an adherend, and therefore, in order to improve weather resistance, it is preferable that the release layer contains a weather resistance agent such as an ultraviolet absorber and a light stabilizer. In this embodiment, it is more preferable that the release layer contains an ultraviolet absorber and a light stabilizer in order to improve light resistance.

[0090] As the ultraviolet absorbing agent and the light stabilizer, general-purpose compounds can be used. Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers, and among these, hydroxyphenyltriazine ultraviolet absorbers are preferred. Hydroxyphenyltriazine compounds are less likely to bleed out from the release agent, that is, from the cured product of the resin composition for forming the release layer. Therefore, the deterioration of the aesthetic appearance of the surface of the decorative material after transfer, such as the ultraviolet absorber bleeding out and causing stickiness, is suppressed, and not only is the aesthetic appearance maintained well, but the bleed-out ultraviolet absorber is gradually lost due to rain runoff, etc., and the concentration of the ultraviolet absorber in the release layer decreases over time, which suppresses the decrease in weather resistance, and excellent light resistance can be obtained over a long period of time.

[0091] Preferred examples of the light stabilizer include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers, and among these, hindered amine compounds are preferred. Furthermore, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond in the molecule, such as a (meth)acryloyl group, a vinyl group, or an allyl group, because they are less likely to bleed out due to the reaction with the curable resin preferably used in the formation of the release agent.

[0092] The content of the ultraviolet absorber in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 1 part by mass or more and 7 parts by mass or less, relative to 100 parts by mass of the resin of the release layer. The content of the light stabilizer in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and even more preferably 1 part by mass or more and 7 parts by mass or less, based on 100 parts by mass of the resin in the release layer.

[0093] In order to improve the handleability of the transfer sheet and the scratch resistance and weather resistance of the release layer, the thickness of the release layer is preferably 1.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and even more preferably 3 μm or more and 15 μm or less.

[0094] [Adhesive layer] The release layer is a layer formed as necessary to facilitate the transfer of the transfer layer to the adherend. For example, when transferring the transfer layer of the transfer sheet to the adherend, if a separately prepared adhesive is used between the adherend and the transfer sheet, the transfer layer does not need to have an adhesive layer. In addition, if the transfer layer and the adherend can be adhered to each other without using an adhesive, the transfer layer does not need to have an adhesive layer. When the transfer layer has an adhesive layer, it is preferable to form the adhesive layer at a position farthest from the releasable support among the layers constituting the transfer layer. The adhesive layer can also function as a decorative layer described later.

[0095] The adhesive layer may be a pressure-sensitive adhesive layer, a curable adhesive layer, or a heat-sensitive adhesive layer. Among these, a heat-sensitive adhesive layer is preferred in order to improve the handling of the transfer sheet and the adhesion between the transfer layer and the adherend. The heat-sensitive adhesive layer may also be called a heat seal layer.

[0096] When the adhesive layer is a pressure sensitive adhesive layer, it is preferred that the adhesive layer contains a pressure sensitive adhesive. The adhesive may be appropriately selected from acrylic, urethane, silicone, rubber, and other adhesives.

[0097] When the adhesive layer is a curable adhesive layer, it is preferable that the adhesive layer contains a thermosetting adhesive. The thermosetting adhesive is preferably one that contains a composition that has the property of crosslinking by a chemical reaction caused by heat, and examples of such adhesives include two-component curing urethane adhesives, polyester urethane adhesives, polyester urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, etc. The urethane resin that constitutes the two-component curing urethane adhesive is a polyurethane that uses polyol (polyhydric alcohol) as the main component and isocyanate as the crosslinking agent (curing agent).

[0098] When the adhesive layer is a heat-sensitive adhesive layer, it is preferred that the adhesive layer contains a thermoplastic resin. Examples of the thermoplastic resin include acrylic resin, urethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, polyester resin, amide resin, cyanoacrylate resin, epoxy resin, etc., which can be used alone or in combination. Among these, acrylic resin, which has good weather resistance, is preferred.

[0099] The weight average molecular weight of the thermoplastic resin is preferably 10,000 to 200,000, more preferably 50,000 to 150,000, and more preferably 80,000 to 120,000. When the weight average molecular weight of the thermoplastic resin is within the above range, the coating suitability is improved, and the adhesive layer is easily formed in a good condition. Furthermore, when the weight average molecular weight of the thermoplastic resin is within the above range, the adhesion between the adhesive layer and the adherend can be easily improved.

[0100] The thickness of the adhesive layer is preferably from 1 μm to 10 μm, more preferably from 2 μm to 8 μm, and even more preferably from 3 μm to 7 μm. When the thickness of the adhesive layer is within the above range, it is easy to improve the adhesion between the adhesive layer and the adherend, and it is easy to improve the handleability of the transfer sheet.

[0101] The adhesive layer may contain a colorant, if necessary. By including a colorant in the adhesive layer, the adhesive layer alone, or in combination with the decorative layer described below, can enhance the design of the transfer layer and improve the concealing properties of the transfer layer, thereby concealing the color and appearance of the surface of the adherend.

[0102] The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black; metal pigments such as scaly foil flakes of aluminum, brass, and the like; and pearlescent pigments such as scaly foil flakes of titanium dioxide-coated mica, basic lead carbonate, and the like.

[0103] The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 20 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the resin constituting the adhesive layer. By making the content of the colorant 5 parts by mass or more, the design of the transfer layer can be easily improved, and by making the content of the colorant 90 parts by mass or less, the decrease in the adhesive strength of the adhesive layer can be easily suppressed.

[0104] [Primer layer] The transfer layer is formed by: Each layer of the transfer layer may be subjected to a surface treatment such as physical surface treatment such as the oxidation method or roughening method described above, or a chemical surface treatment, if necessary. A primer layer may be provided between each of these layers as an easy-adhesion layer, or these surface treatments may be combined and used. The primer layer may be formed, for example, between the release layer and the adhesive layer. When the primer layer and the decorative layer are present between the release layer and the adhesive layer, it is preferable that the primer layer is positioned closer to the release layer than the decorative layer. By forming the primer layer between the release layer and the adhesive layer, the interlayer adhesion of the transfer layer is improved, and the weather resistance and durability of the transfer layer can be improved.

[0105] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.

[0106] Preferred examples of the binder resin include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and having two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), cellulose acetate resin, and the like. These may be used alone or in combination of two or more kinds. The binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the above resin and crosslinking and curing the resin. Among these, polycarbonate-based urethane-acrylic copolymers are preferred.

[0107] The polycarbonate-based urethane acrylic copolymer can be obtained, for example, by the following steps (1) and (2). The polycarbonate-based urethane acrylic copolymer is preferable in that it has good flexibility, easily follows the cure shrinkage of the release layer, has good weather resistance, etc. (1) A polycarbonate-based polyurethane polymer is obtained by reacting a polycarbonate diol with a (di)isocyanate. (2) The polycarbonate-based polyurethane polymer and an acrylic monomer are radically polymerized to obtain a polycarbonate-based urethane acrylic copolymer.

[0108] Examples of the (di)isocyanate include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanatophenylsulfonyl isocyanate, and o- or p-isocyanatophenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; alicyclic isocyanates; and the like.

[0109] Examples of the acrylic monomer include (meth)acrylic acid, alkyl (meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0110] The mass ratio of the acrylic component to the urethane component in the polycarbonate-based urethane acrylic copolymer is preferably 30 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 85 parts by mass or more, and the upper limit is preferably 95 parts by mass or less, more preferably 93 parts by mass or less, and even more preferably 90 parts by mass or less, relative to 100 parts by mass of the total amount of the acrylic component and the urethane component. By setting the mass ratio of the acrylic component to the urethane component within the above range, the primer layer does not become an excessively hard coating film, and sufficient processability is obtained, and interlayer adhesion with the release layer is good, especially when the release layer is made of a urethane acrylic resin such as a urethane (meth)acrylate oligomer.

[0111] The primer layer preferably contains an anti-blocking agent. Examples of the anti-blocking agent include inorganic particles such as silica, alumina, aluminum hydroxide, barium sulfate, talc, calcium carbonate, and organic particles. Among these, inorganic particles are preferred, and among inorganic particles, silica is preferred.

[0112] The average particle size of the antiblocking agent is preferably about 0.1 to 10 μm, more preferably 0.5 to 8 μm, and further preferably 0.5 to 5 μm. The particle size of the antiblocking agent is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method. The content of the antiblocking agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, further preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass, based on 100 parts by mass of the binder resin.

[0113] The thickness of the primer layer is preferably from 0.5 μm to 10 μm, more preferably from 1 μm to 8 μm, and even more preferably from 2 μm to 6 μm.

[0114] [Decorative layer] The transfer layer may have a decorative layer to enhance the design. The decorative layer is preferably formed between the release layer and the adhesive layer.

[0115] The decorative layer may be formed on the entire surface of the transfer sheet, or may be formed only on a part of the surface.

[0116] Examples of the decorative layer include a colored layer formed by applying ink in a solid manner, a pattern layer formed by printing ink as a pattern, and a thin metal film. Examples of patterns (designs) that can be expressed by the decorative layer include wood grain patterns such as tree rings and vascular grooves on the surface of wooden boards; stone grain patterns on the surface of stone slabs such as marble and granite; fabric grain patterns on the surface of fabric; leather grain patterns on the surface of leather; tile patterns including grooves in the joints; brickwork patterns including grooves in the joints; sand grain patterns; pear-skin patterns; patterns consisting of an arrangement of multiple concave and convex ridges that extend in parallel directions (so-called ``line-like concave and convex patterns'' or ``ray-carved patterns''); and abstract patterns such as geometric patterns, letters, figures, polka dots, and floral patterns.

[0117] The ink used for the colored layer and the design layer is a suitable mixture of a binder resin, a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a hardener, an ultraviolet absorber, a light stabilizer, etc. The binder resin for the colored layer and the design layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins accompanied by a curing agent such as an isocyanate compound.

[0118] The colorant is not particularly limited, and the colorants exemplified for the adhesive layer can be suitably used. The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more and 70 parts by mass or less, based on 100 parts by mass of the resin constituting the decorative layer.

[0119] The color layer and the design layer may contain additives such as an ultraviolet absorbing agent, a light stabilizer, and a coloring agent. The thickness of the colored layer and the patterned layer may be appropriately selected according to the desired pattern, but in order to improve the design, it is preferably 0.5 μm to 20 μm, more preferably 1 μm to 10 μm, and even more preferably 2 μm to 5 μm. In particular, when it is necessary to conceal the color and appearance of the adherend, the thickness of the colored layer and the patterned layer is preferably 1.5 μm or more, although it depends on the type and content of the colorant contained.

[0120] Examples of metal thin films include thin films of simple metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt, thin films of alloys containing two or more of the above metal elements, etc. Examples of alloys include brass, bronze, and stainless steel. The thickness of the thin metal film can be about 0.1 μm or more and 1 μm or less.

[0121] The above-mentioned release layer, primer layer, adhesive layer and decorative layer can be formed, for example, by applying a coating liquid containing a composition for forming each layer onto a releasable support by a known method such as gravure printing, bar coating, roll coating, reverse roll coating or comma coating, and then drying and curing the coating as necessary.

[0122] <separator> The transfer sheet may have a separator on the side of the transfer layer opposite the releasable support. When the adhesive layer is a pressure-sensitive adhesive layer, having a separator on the transfer layer makes it easier to prevent blocking when the transfer sheet is wound into a roll, and makes it easier to prevent the transfer sheet from accidentally sticking to other objects.

[0123] The material of the separator is not particularly limited as long as it is a material that can be peeled off from the transfer layer, and a plastic film is preferably used. The plastic film used as the separator may be the same as that exemplified for the support described above. The surface of the separator that comes into contact with the transfer layer is preferably treated with a release agent or the like. As the release agent, a known release agent such as a fluorine-based release agent or a silicone-based release agent may be used. The thickness of the separator is not particularly limited, but in order to improve the handleability of the transfer sheet, it is preferably from 10 μm to 200 μm, more preferably from 15 μm to 150 μm, and even more preferably from 20 μm to 100 μm.

[0124] [Method for producing releasable support] The releasable support constituting the transfer sheet of the present embodiment can be produced, for example, by the following method. It is preferable to manufacture the release layer through a step of forming a coating layer by applying a resin composition for forming a release layer, which contains a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin, to one main surface side of a support, and a step of forming a release layer by irradiating the coating layer with light having a wavelength of at least 100 nm or more and less than 200 nm to harden the coating layer to form a release layer. In addition, when the resin composition contains a solvent, a solvent drying step may be performed after the step of forming the coating layer.

[0125] The above-mentioned method for producing a transfer sheet can be particularly suitable for producing a transfer sheet capable of imparting a matte effect with a 60° gloss value of 5.0 or less on the release layer side. In particular, the method for producing a releasable support of this embodiment is distinct from the conventionally known methods for producing matte decorative materials in that it is possible to realize a matte (low gloss, low luster) surface with a 60° gloss value of 5.0 or less by suppressing the amount of μm-order particles added to a low content of 15 parts by mass or less per 100 parts by mass of resin. By such a manufacturing method, the releasable support of the present embodiment can be easily obtained. Specifically, in forming the release layer, by irradiating the resin composition containing the wrinkle formation stabilizer forming the release layer with ultraviolet light having a short wavelength of at least 100 nm or more and less than 200 nm, wrinkles can be formed on at least one surface of the release layer, and the visibility and texture of the matte effect can be stably imparted to the surface of the release support (≒ the surface of the release layer).

[0126] The details of the mechanism by which irradiating the resin composition for forming the release layer with such low-wavelength ultraviolet light stabilizes the formation of wrinkles on at least one surface of the release layer, thereby stably expressing the visibility and texture of the matte effect, are unknown, but it is presumed to be due to the following mechanism.

[0127] When a coating in which a resin composition for forming a release layer is applied to a predetermined thickness is irradiated with ultraviolet light of a short wavelength, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition begins to harden, and it is considered that wrinkles are formed due to the occurrence of hardening shrinkage only on the surface. In this way, it is considered that the stable formation of wrinkles occurs when the resin composition for forming a release layer is hardened only in a certain thickness direction from the surface by irradiation with ultraviolet light of a short wavelength. In addition, by comparing the examples and comparative examples described below, when the wrinkle formation stabilizer is not included, the formation of wrinkles becomes unstable and the visibility of the matte effect is not stable and sufficiently expressed over the entire surface of the release layer, so the stable expression of the matte effect cannot be explained by only hardening of the surface part by low-wavelength ultraviolet light. That is, in order for the transfer sheet of this embodiment to stably have wrinkles and thereby exhibit the visibility of the matte effect, it is essential that the wrinkle formation stabilizer is included. Considering that the stable visibility of the matte effect due to the stable formation of wrinkles is not obtained when the wrinkle formation stabilizer is not included, it is considered that the wrinkle formation stabilizer has a function like a nucleus that triggers the formation of wrinkles, and the resin of the surface part of the resin composition gathers around the nucleus to form the convex part (protrusion part) of the wrinkles and the formation of the convex part (protrusion part) and the formation of the concave part are formed, and as a result, the formation of the wrinkles is stabilized. And, it is considered that the wrinkles formed in this way stably impart the visibility of the matte effect to the surface of the releasable support and also stably impart texture due to the light diffusion effect caused by the shape.

[0128] The wrinkle formation stabilizer and the resin composition for forming a release layer containing the wrinkle formation stabilizer used in this manufacturing method are the same as those described above as the wrinkle formation stabilizer and the resin composition for forming a release layer that can be used in the release layer of this embodiment.

[0129] In this manufacturing method, it is preferable to irradiate the resin composition for forming the release layer with light having a wavelength of at least 100 nm or more and less than 200 nm. By this irradiation, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition begins to harden, and the formation of wrinkles is stabilized by the occurrence of hardening shrinkage only on the surface, and the surface layer of the resin composition becomes a hardened product having wrinkles. Then, after this, hardening proceeds from the surface vicinity portion where hardening proceeds slowly to the deep portion distant in the depth direction, and the resin composition is hardened over the entire thickness, and a release layer having wrinkles that exhibit a light diffusion effect on the surface is formed. From the viewpoint of promoting the progress of hardening to the deep portion, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of at least 100 nm and less than 200 nm, as described below.

[0130] As the light having a wavelength of at least 100 nm and less than 200 nm, for example, rare gases such as Ar, Kr, Xe, Ne, halogenated rare gases such as F, Cl, I, Br, or the like, or excited dimers formed by discharging a mixed gas of these gases, that is, "excimer light" including light in the ultraviolet wavelength region from excimers. As the wavelength of the excimer light and the excimer as the light source, for example, light having a wavelength of 126 nm radiated from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), and the like can be preferably adopted. As the excimer light, either spontaneous emission light or laser light with high coherence (coherence) due to stimulated emission can be used, but it is usually sufficient to use spontaneous emission light. Incidentally, a discharge lamp that emits the light (ultraviolet light) is also called an "excimer lamp". Excimer light has a single wavelength peak and is characterized by a narrower half-width wavelength than ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.) By using such excimer light, wrinkle formation is stabilized, and the visibility and texture of the matte effect are stably improved.

[0131] From the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more, with the upper limit being less than 200 nm, and particularly preferably 172 nm (Xe2). Thus, in the present manufacturing method, from the viewpoint of stably improving the visibility and texture of the matte effect, it is preferable to use light with a shorter wavelength, and it can be said that, among low-wavelength ultraviolet rays (wavelength: 280 nm or less), low-wavelength ultraviolet rays in the region of less than 200 nm are preferable.

[0132] In the present production method, the integrated light amount of the light of the above wavelength is preferably 1 mJ / cm from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect. 2 More preferably, 10 mJ / cm 2 More preferably, 30 mJ / cm 2 More preferably, 50 mJ / cm 2 The upper limit is not particularly limited, but from the viewpoint of productivity, such as reducing the number of lamps required for irradiation of wavelength light and improving production efficiency, the upper limit is preferably 1,000 mJ / cm 2 Less than or equal to 500 mJ / cm 2 More preferably, 300 mJ / cm 2 The following is the result. From the same viewpoint, the ultraviolet light output density is preferably 0.01 W / cm or more, more preferably 0.1 W / cm or more, and even more preferably 0.5 W / cm or more, and the upper limit is preferably 10 W / cm or less, more preferably 5 W / cm or less, and even more preferably 3 W / cm or less. In addition, the oxygen concentration during irradiation with light of the above wavelengths is preferably lower, and is preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

[0133] In the release layer forming step in the present production method, in addition to the irradiation with light having a wavelength of at least 100 nm and less than 200 nm, other treatments that contribute to hardening of the resin composition for forming the release layer may be carried out. For example, in order to stabilize the formation of wrinkles due to the difference in the degree of curing between the surface portion and the deep portion distant from the surface in the depth direction, and to promote the progress of curing to the deep portion, the resin composition for forming the release layer may be pre-cured as a whole by irradiating the resin composition with light having a wavelength of 200 nm or more, for example, light having a wavelength of 380 nm or more, preferably light having a wavelength of about 385 nm or more and 400 nm or less, and then irradiated with light having a wavelength of 100 nm or more and less than 200 nm, or post-curing may be performed to further cure the resin composition after irradiation with light having a wavelength of 100 nm or more and less than 200 nm. The necessity of pre-curing and post-curing may be appropriately determined depending on the desired properties required for the release layer (for example, surface properties such as scratch resistance and contamination resistance, and processing properties). In addition, although the above-mentioned wavelength light belongs to ultraviolet rays, it is also possible to use other ionizing radiations other than ultraviolet rays, such as electron beams. For example, in post-curing, electron beams may be preferably used to improve the durability of the release layer.

[0134] In this manufacturing method, the release layer can be formed by irradiating a coating layer (uncured resin layer) prepared by applying a resin composition for forming the release layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, with light having a wavelength of at least 100 nm and less than 200 nm.

[0135] [Manufacturing method of decorative materials] The method for producing a decorative material of the present embodiment includes the following steps (1) and (2). (1) A step of obtaining a laminate by closely adhering the transfer layer side of the transfer sheet of the present embodiment described above to an adherend. (2) A step of peeling off the releasable support from the laminate to obtain a decorative material having a transfer layer on an adherend.

[0136] In the transfer sheet of this embodiment, the surface shape of the releasable support (≒ surface shape of the release layer) has the visibility and texture of the matte effect. The surface shape of the release layer is reflected in the surface shape of the transfer layer. Therefore, according to the manufacturing method of the decorative material of this embodiment using the transfer sheet of this embodiment, a decorative material with excellent visibility and texture of the matte effect can be obtained.

[0137] [Adherent material] The adherend in step (1) is not particularly limited, and can be appropriately selected from adherends made of fibrous materials such as paper, nonwoven fabric and woven fabric, resins, wood-based materials, metals, nonmetallic inorganic materials, and the like. The form (or shape) of the adherend is not particularly limited and may be a film, sheet, plate, polyhedron, polygonal prism, cylinder, cone, sphere, spheroid, etc. The film, sheet, and plate are the same as those described above for the support.

[0138] Similarly to the support, the adherend may be a single layer, or may be a laminate of two or more layers made of the above materials. When the adherend is a laminate of two or more layers, it is preferable that the layers are made of different materials and the properties of the materials in each layer are mutually complemented. Examples of substrates made of two or more layers are: In addition to the laminates (1) to (3) exemplified above as the support, the following laminates (4) to (9) are also included, where " / " indicates the interface between the layers. (4) Resin / Metal (5) Resin / fibrous materials (6) Metal / wood materials (7) Metal / non-metal inorganic materials (8) Metal / fibrous materials (9) Metal 1 / Metal 2 (for example, when there are multiple layers in which Metal 1 is copper and Metal 2 is chromium)

[0139] The adherend made of fibrous materials such as paper, nonwoven fabric and woven fabric, resin, or wood-based material may be appropriately selected from the materials described above as the support. Examples of metals include aluminum, aluminum-containing alloys such as duralumin, iron-containing alloys such as iron, carbon steel, and stainless steel, copper-containing alloys such as copper, brass, and bronze, gold, silver, chromium, nickel, cobalt, tin, titanium, etc. Furthermore, as the metal substrate made of a metal, those which have been subjected to a treatment such as plating of these metals can also be used. Further, examples of non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (aerated lightweight concrete), gypsum, calcium silicate, and wood chip cement, ceramic ceramic materials such as pottery, earthenware, glass, and enamel, and natural stones such as limestone (including marble), granite, andesite, etc.

[0140] Other possible forms of the support are the same as those described above for the support, such as that the base material may be colored, that additives may be incorporated, that a surface treatment may be applied, or that a primer layer may be formed.

[0141] In step (1), the transfer layer side of the transfer sheet and the adherend can be adhered to each other, for example, by an adhesive layer of the transfer layer. If the transfer layer does not have an adhesive layer, an adhesive may be interposed between the transfer layer and the adherend in step (1).

[0142] One embodiment of the step (1) is a method using a lamination method having the following steps (a1) and (a2) in this order: (a1) A step of contacting and overlapping the transfer layer side of the transfer sheet on a flat substrate. (a2) A step of applying heat and / or pressure from the release film side of the transfer sheet to bring the adherend on the flat plate and the transfer layer of the transfer sheet into close contact with each other.

[0143] Another embodiment of step (1) is an in-mold molding method that requires the following steps (z1) to (z4) in order: In the in-mold molding, the resin poured in step z2 becomes the adherend. (z1) A step of placing the transfer layer side of the transfer sheet facing the inside of the in-mold molding die. (z2) A step of injecting a resin into the in-mold molding die. (z3) A step of integrating the transfer sheet and the resin to bring the transfer layer of the transfer sheet and the resin into close contact with each other to form a resin molded body. (z4) A step of removing the resin molded body from the in-mold molding die.

[0144] When the transfer sheet has a separator on the side of the transfer layer opposite to the releasable support, it is preferable to have the following step (0) before the above step (1). (0) A step of peeling off the separator from the transfer sheet.

[0145] The decorative material obtained as described above can be cut as desired, and the surface or end of the wood can be decorated as desired, such as by groove processing or chamfering, using a cutting machine such as a router or cutter. It can be suitably used for various applications, such as interior components for buildings, such as walls, ceilings, and floors; exterior components, such as exterior walls, eaves ceilings, roofs, fences, and fences; fixtures or fittings, such as window frames, doors, door frames, handrails, baseboards, moldings, and other fittings; general furniture, such as chests of drawers, shelves, and desks; kitchen furniture, such as dining tables and sinks; various furniture and components used in wet areas, such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets, home appliances, office automation equipment, and the like; interior and exterior components for vehicles; signboards; and various components, such as soundproof walls. Furthermore, in addition to the various components described above, the decorative material can be used alone or in a form laminated or composited with other materials for packaging materials, antiglare films for displays, white or black boards, various cards such as credit cards, cash cards, telephone cards, and various certificates, keys of various keyboards, transparent panels such as windows, doors, and partitions (window glass, show windows, etc.), artificial leather, etc. In other words, the transfer sheet of this embodiment is suitably used as a transfer sheet for transferring a transfer layer such as a concave-convex shape and a pattern layer to these various components, etc. Among the decorative materials, the resin decorative board is preferably used mainly as a surface decorative board for general furniture such as chests, shelves, and desks, as well as for fittings such as doors, and as various counters. EXAMPLES

[0146] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0147] 1. Evaluation 1-1.60° gloss value A sample was prepared by bonding a black plate to the back of the polycarbonate resin plate of the decorative material obtained in the examples and comparative examples via an adhesive layer. The 60° specular gloss of the sample was measured from the release layer side using a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner Co., Ltd.) in accordance with JIS K5600-4-7:1999.

[0148] 1-2. Evaluation of texture before weather resistance test The cosmetic materials obtained in the Examples and Comparative Examples were evaluated for surface texture (uniformity of surface condition) by 20 random adults, and were rated according to the following criteria. A: 18 or more panelists rated the surface condition as uniform and the matte effect as highly visible. B: 15 or more and 17 or less judged that the surface condition was uniform and the matte effect was highly visible. C: 14 or less panelists rated that the surface condition was uniform and the matte effect was highly visible.

[0149] 1-3. Evaluation of texture after weather resistance test The decorative materials obtained in the Examples and Comparative Examples were subjected to the following weather resistance test. After the weather resistance test, the surface texture (uniformity of surface condition) of the decorative materials was evaluated using the same criteria as in 1-2. <Weather resistance test> A weather resistance test was carried out using a weather resistance test device (manufactured by Daipla Wintes Co., Ltd. under the trade name "Metal Weather"). In the weather resistance test, the following "ultraviolet light irradiation process", "condensation process", and "water spray process" were defined as one cycle, and the cycle was repeated for 500 hours. 《Ultraviolet irradiation process》 Illuminance: 60mW / cm 2, Black panel temperature: 63℃, chamber humidity: 50%RH, time: 20 hours 《Condensation process》 Illuminance: 0mW / cm 2 , Black panel temperature: 30℃, Humidity inside the chamber: 98%RH, Time: 4 hours 《Water spray process》 Spray water for 10 seconds before and after the condensation process.

[0150] 2. Preparation of transfer sheets and preparation of decorative materials using transfer sheets [Example 1] A resin composition containing an acrylic resin and a urethane resin as binder resins was applied to one surface of a support (a corona discharge-treated PET sheet, thickness: 100 μm) and dried to form an easy-adhesion layer (thickness: 2 μm). The following resin composition for forming a release layer was applied onto the easy-adhesion layer by a gravure method (application amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light amount: 0.6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet light output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 , a nitrogen atmosphere (oxygen concentration 200 ppm or less), and then ultraviolet light was irradiated using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm) to form a release layer. Through the above steps, a releasable support having an easy-adhesion layer and a release layer on the support was obtained.

[0151] Next, the following resin composition 1 for forming a release layer was applied onto the release layer of the releasable support to form an uncured resin layer, and the uncured resin layer was cured by irradiating it with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to form a release layer (thickness: 5 μm). Then, corona irradiation was performed on the release layer. Next, the following resin composition for forming a primer layer was applied onto the corona-irradiated release layer and dried to form a primer layer having a thickness of 2.5 μm. Next, an acrylic resin (PMMA, weight average molecular weight: 96,000) was applied onto the primer layer and dried to form a 4 μm thick adhesive layer having heat sealability. After forming the adhesive layer agent, it was aged at room temperature for 24 hours to obtain a transfer sheet of Example 1.

[0152] The adhesive layer of the transfer sheet of Example 1 was placed opposite one side of the adherend, a polycarbonate plate (thickness: 2 mm, manufactured by AGC, product name "Carbo Polish"), and laminated. Then, using a laminator (roll-type thermal transfer machine, "RT-300 (model number)", manufactured by Navitas Co., Ltd.), the transfer sheet was heated and pressed at a lamination roll temperature of 160°C and a conveying speed of 1.5 m / min, to obtain a laminate in which the transfer layer of the transfer sheet and the adherend were in close contact with each other. Next, the release film was peeled off from the laminate to obtain the decorative material of Example 1. The decorative material of Example 1 has a transfer layer on the adherend.

[0153] <Resin composition for forming release layer> Multifunctional urethane acrylate oligomer (4 functional): 65 parts by weight Monofunctional acrylate monomer: 35 parts by weight Wrinkle formation stabilizer (silica particles, average particle size: 3 μm): 1.0 parts by weight Photopolymerization initiator (benzophenone type): 0.8 parts by weight

[0154] <Resin composition 1 for forming release layer> Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 100 parts by weight Ultraviolet absorber (BASF, product name: Tinuvin 479): 0.5 parts by weight Light stabilizer (BASF, product name: Tinuvin 123): 0.3 parts by mass

[0155] <Resin composition for forming primer layer> Polycarbonate-based urethane acrylic copolymer: 100 parts by weight (Weight average molecular weight 50,000) Ultraviolet absorber (BASF, product name: Tinuvin 479): 20 parts by weight Ultraviolet absorber (BASF, product name: Tinuvin 400): 15 parts by weight Light stabilizer (BASF, product name: Tinuvin 123): 3.5 parts by mass Anti-blocking agent (silica with an average particle size of 3 μm): 10 parts by weight Solvent: appropriate amount

[0156] [Examples 2 to 3] Transfer sheets of Examples 2 and 3 were obtained in the same manner as in Example 1, except that the amount of the wrinkle formation stabilizer in the resin composition for forming the release layer in Example 1 was changed to the amount shown in Table 1. Using the obtained transfer sheets, decorative materials of Examples 2 and 3 were obtained in the same manner as in Example 1.

[0157] [Example 4] In Example 1, the amount of the wrinkle formation stabilizer in the resin composition for forming the release layer was changed to the amount shown in Table 1. Furthermore, the resin composition 1 for forming the release layer was changed to the following resin composition 2 for forming the release layer. A transfer sheet of Example 4 was obtained in the same manner as in Example 1, except for the above-mentioned changes. Using the obtained transfer sheet, a decorative material of Example 4 was obtained in the same manner as in Example 1.

[0158] <Resin composition 2 for forming release layer> Ionizing radiation curable resin (2-functional urethane acrylate oligomer and 6-functional urethane acrylate oligomer in a mass ratio of 4:6): 100 parts by mass Ultraviolet absorber (BASF, product name: Tinuvin 479): 2 parts by weight Light stabilizer (Nippon Nyukazai Co., Ltd., product name: Sanol LS-3410): 3 parts by weight

[0159] [Comparative Example 1] A transfer sheet was obtained in the same manner as in Example 1, except that the amount of the wrinkle formation stabilizer in the resin composition for forming the release layer was set to 0 parts by mass in Example 1. A decorative material was obtained in the same manner as in Example 1 using the obtained transfer sheet.

[0160] [Comparative Example 2] In Example 1, the amount of wrinkle formation stabilizer in the resin composition for forming the release layer was 0 parts by mass, and instead, 15.0 parts by mass of a matting agent (average particle size: 5.0 μm) was used, and ultraviolet rays were irradiated using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm). A transfer sheet was obtained in the same manner as in Example 1. A decorative material was obtained in the same manner as in Example 1 using the obtained transfer sheet.

[0161] [Comparative Example 3] One side of a support (PET with a thickness of 100 μm) was subjected to sandblasting. Next, a release layer, a primer layer, and an adhesive layer were formed on the sandblasted surface in the same manner as in Example 1 to obtain a transfer sheet of Comparative Example 3. Next, a decorative material was obtained in the same manner as in Example 1 using the obtained transfer sheet.

[0162] [Table 1]

[0163] From the results in Table 1, it was confirmed that the decorative materials obtained using the transfer sheets of Examples 1 to 4 had 60° gloss values ​​of 1.4 to 1.8, and thus had extremely excellent visibility of the matte effect. On the other hand, the decorative material obtained using the transfer sheet of Comparative Example 1, which does not contain a wrinkle formation stabilizer in the release layer, had some wrinkles on its surface as shown in Figure 7, but did not provide a stable matte effect and was not able to provide an excellent texture. The decorative sheet of Comparative Example 2, which contains a matte agent in the release layer, contained 15.0 parts by mass, which is greater than the amount of the wrinkle formation stabilizer in the Examples, but no wrinkles were formed in the surface layer corresponding to the release layer, and the 60° gloss value of the decorative material obtained using this was 8.3, which was inferior to the gloss value of the decorative material of the Examples, despite the use of a larger amount of matte agent than the wrinkle formation stabilizer in the Examples, and it was confirmed that the texture was also inferior. In addition, the decorative material obtained using the transfer sheet of Comparative Example 3, which contained a sandblasted support, had a high 60° gloss value of 21.4 and was inferior in matte effect.

[0164] In addition, according to the optical microscope images (FIGS. 4 to 6, respectively) of the release layer side surface of the releasable support of Examples 1 to 3, it can be confirmed that the transfer sheets of these Examples have uniform irregular wrinkles on the surface of the release layer. On the other hand, according to the optical microscope image of Comparative Example 1 (FIG. 7), as already described, wrinkles are slightly generated on the surface, and although there are some areas with wrinkles similar to those of the Examples, the formation of wrinkles is unstable (not uniform), and it can be seen that they are mixed with areas without wrinkles. In addition, according to the optical microscope image of Comparative Example 2 (FIG. 8), wrinkles like those of the transfer sheets of the Examples were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From these results, it was confirmed that the transfer sheet of this embodiment exhibits extremely excellent visibility of the matting effect due to the wrinkles on its surface. [Explanation of symbols]

[0165] 100: Transfer sheet 10: Releasable support 11:Support 12: Release layer 20: Transfer layer 21: Release layer 22: Primer layer 23:Decorative layer 24: Adhesive layer 2: Recess 3: Convex part (protrusion)

Claims

[Claim 1] A transfer sheet having a transfer layer on a releasable support, The releasable support has a release layer on a support, The release layer is composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin, the surface of the release layer facing the transfer layer has an uneven shape composed of irregular wrinkles, and the 60° gloss value of the release layer is 5.0 or less.

Images