Transfer sheet, and manufacturing method of cosmetic material using the same, and cosmetic material

Abstract

To provide a transfer sheet having visibility of an excellent matt effect and a texture, while excellent in rough tactile feeling, and also to provide a production method of a decorative material using the same and a decorative material.SOLUTION: A transfer sheet includes, in at least a part of a surface, a surface shape in which an Spc (an arithmetic average curvature of projection-part apexes) stipulated by JIS B0601:2013 is larger than 4000 mm-1 and an Rsm (an average length of curve elements) is 30 μm or more, and an Spc (an arithmetic average curvature of projection-part apexes) stipulated by JIS B0601:2013 is larger than 4000 mm-1 and an Rsm (an average length of curve elements) is 30 μm or more. A production method of a decorative material using the same and a decorative material are also provided.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Conventionally, decorative materials or decorative sheets have been used as articles for decorating and protecting the surfaces of, for example, interior building components such as walls, ceilings, and floors; exterior building 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 fittings; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative panels for cabinets and the like of home appliances and office automation equipment; and interior or exterior vehicle components. Such decorative materials include, for example, those having a surface layer with desired functions.

[0003] For decorative materials used in these applications, a technique of improving texture by using a matte effect (matt effect) to enhance their design is commonly used. For example, Patent Document 1 proposes a decorative sheet as a decorative material using a matte effect, which has a pattern layer and a concealing layer on one side of a base sheet and a gloss-adjusting layer (matt layer, gloss layer) on the other side. The decorative sheet of Patent Document 1 achieves a design effect by highlighting the pattern layer and the concealing layer due to the difference in gloss between the matte layer and the gloss layer of the gloss-adjusting layer. In an example, the matte layer provided on the entire surface uses a matte ink containing 50 parts by weight of matting agents, namely, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, per 100 parts by weight of resin.

[0004] Furthermore, Patent Document 2 proposes a decorative material having a printed layer and a transparent resin layer in this order on a substrate, with an embossed pattern on the outermost surface of the transparent resin layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-062081 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-073207 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0006] Examples of methods for improving texture by a matte effect include a method in which a matting agent (also referred to as a "matting agent") is used to obtain a matte effect by the light diffusion effect of the agent itself, as in Patent Document 1, and a method in which an embossing process is performed to form an uneven shape on the outermost surface, as in Patent Document 2. However, when a matting agent is used as in Patent Document 1, the amount used must be increased to improve the matting effect. However, as the amount used increases, the matting agent tends to fall off the coating film, damaging the coating film and reducing scratch resistance. Furthermore, scratches become more noticeable due to changes in gloss caused by the loss of the matting agent. Contaminants may penetrate into the minute gaps at the interface between the matting agent and the resin, and the matting agent itself may adsorb contaminants, reducing stain resistance. On the other hand, reducing the amount used to prevent the deterioration of surface properties tends to reduce the matting effect. Therefore, surface properties and matting effect are in a trade-off relationship. Therefore, there are limitations to the matte effect achieved using a matting agent.

[0007] Furthermore, when using embossing as in Patent Document 2, preparing an embossing plate is laborious and not easy, and a plate must be prepared for each desired pattern. Therefore, it cannot be said that this method is easy to fully meet the diverse needs of customers. Furthermore, the embossing method in Patent Document 2 may restrict the manufacturing process, and depending on the material of the item to which the textured pattern is to be applied, it may be difficult to apply the textured pattern. Furthermore, depending on the combination of the type of substrate to be embossed, the embossing conditions, and the textured pattern on the embossing plate, the matte textured pattern on the embossing plate may not be faithfully transferred onto the substrate, resulting in insufficient matte finish.

[0008] However, customer demands are becoming more diverse, and they are now seeking not only the visual matte effect described above, but also a tactile feel. For example, when using a matting agent as in Patent Document 1, increasing the amount used can cause the contours of the matting agent to appear on the surface of the decorative sheet, resulting in a somewhat rough surface feel, i.e., a "grainy" feel. Furthermore, when embossing is used as in Patent Document 2, a tactile feel can be created due to the uneven surface shape created by the embossing plate. However, neither of these methods focuses on the expression of the tactile feel, and it cannot be said that a sufficient expression of the tactile feel has been achieved. In other words, conventional decorative sheets and decorative materials have not been able to achieve both an excellent matte effect and a good tactile feel. In the present invention, we focus on the "grainy" feel, among other tactile feel characteristics.

[0009] The present invention aims to provide a transfer sheet that can impart excellent visibility and texture of a matte effect and a rough feel to the touch, a method for producing a cosmetic material that has excellent visibility and texture of a matte effect and a rough feel to the touch, and the cosmetic material. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention provides the following [1] to

[14] . [1] A transfer sheet having a transfer layer on a releasable support, At least a part of the surface of the transfer layer on the side of the releasable support is ISO25178 The Spc (arithmetic mean curvature of the apex of the protrusion) specified in -1 A transfer sheet having a surface shape larger than the above, with an Rsm (average length of curved elements) as defined in JIS B0601:2013 of 30 μm or more. [2] The transfer sheet according to [1], wherein the surface shape has a profile peak and height parameter Rz (maximum height) defined in JIS B0601:2013 of 8.00 μm or more and 30.00 μm or less. [3] A transfer sheet according to [1] or [2], wherein the surface shape has a Ra (arithmetic mean roughness), which is a parameter in the height direction of the profile curve as defined in JIS B0601:2013, of 1.00 μm or more and 5.50 μm or less.

[0011] [4] The transfer sheet according to any one of [1] to [3], wherein the surface of the transfer layer that forms the surface shape has an uneven shape formed by irregular wrinkles. [5] The transfer sheet described in [4], wherein the irregular wrinkles are composed of 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. [6] The transfer sheet according to any one of [1] to [5], wherein the transfer layer has a release layer and an adhesive layer in this order from the releasable support side.

[0012] [7] The transfer sheet according to [6], which has one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. [8] The transfer sheet according to [6] or [7], wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation curable resin. [9] The transfer sheet according to any one of [6] to [8], wherein the release layer contains an ultraviolet absorber or a light stabilizer.

[0013]

[10] The transfer sheet according to any one of [6] to [9], wherein the release layer is substantially free of particles.

[11] The transfer sheet according to any one of [1] to

[10] , wherein the releasable support has a release layer on the support.

[12] The transfer sheet according to

[11] , wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation curable resin.

[13] 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 of the transfer sheet according to any one of [1] to

[12] 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 the adherend.

[14] A decorative material having a transfer layer on an adherend, At least a part of the surface of the transfer layer opposite to the adherend is ISO25178 The Spc (arithmetic mean curvature of the apex of the protrusion) specified in -1 A decorative material having a surface shape that is larger than the above and has an Rsm (average length of curved elements) specified in JIS B0601:2013 of 30 μm or more. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a transfer sheet that can impart excellent visibility and texture of a matte effect and a rough feel to the touch. Furthermore, according to the present invention, it is possible to easily produce a decorative material that has excellent visibility and texture of a matte effect and a rough feel to the touch. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 2 is a schematic diagram illustrating the surface shape of the transfer sheet of the present invention. [Figure 2] FIG. 2 is a schematic diagram illustrating the surface shape of the transfer sheet of the present invention. [Figure 3] 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention. [Figure 4] 1 is a schematic plan view illustrating one embodiment of a transfer sheet of the present invention. [Figure 5] 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention. [Figure 6] 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present invention. [Figure 7] 1 is an optical microscope image of the surface of the decorative material obtained in Example 1. [Figure 8] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 1. [Figure 9] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 2. [Figure 10] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 3. [Figure 11] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 4. [Figure 12] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 5. [Figure 13] 1 is an optical microscope image of the surface of the decorative material obtained in Comparative Example 6. DETAILED DESCRIPTION OF THE INVENTION

[0016] [Transfer sheet] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values ​​associated with "greater than or equal to," "less than or equal to," and "to" in describing a numerical range 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.

[0017] The transfer sheet of the present embodiment has a transfer layer on a releasable support, and at least a part of the surface of the transfer layer on the releasable support side has a projection apex having an arithmetic mean curvature Spc (the arithmetic mean curvature of the apex of the protrusion) of 4000 mm -1 The surface is characterized by having a surface shape with a Rsm (average length of curved elements) of 30 μm or more.

[0018] Fig. 3 is a cross-sectional view showing one embodiment of a transfer sheet 100 of the present invention. The transfer sheet 100 in Fig. 3 has a transfer layer 20 on a releasable support 10. Also in Fig. 3, the releasable support 10 has a release layer 12 on a support 11. Also in Fig. 3, the transfer layer 20 has, in this order from the side closest to the releasable support 10, a peel layer 21, a primer layer 22, a decorative layer 23, and an adhesive layer 24.

[0019] In the transfer sheet of Fig. 3, a peeling layer 21 is located on the releasable support 10 side of the transfer layer 20. Therefore, in the transfer sheet of Fig. 3, at least a part of the surface of the peeling layer 21, which is the surface of the transfer layer 20 on the releasable support 10 side, has a curvature of 4000 mm (arithmetic mean curvature of the apex of the protrusions). -1The surface shape is larger than the surface roughness, and has a Rsm (average length of curved elements) of 30 μm or more.

[0020] [Surface shape] The transfer sheet of this embodiment will be described starting with the surface shape of at least a part of the surface of the transfer layer on the releasable support side (hereinafter also simply referred to as "surface shape of the transfer layer" or "surface shape"). The surface shape of the transfer layer is reflected in the surface shape of the decorative material obtained by transferring the transfer layer to an adherend. As mentioned above, the surface shape of the transfer layer is reflected in the surface shape of the decorative material obtained by transferring the transfer layer to an adherend, but the surface shape of the transfer layer and the surface shape of the decorative material are not limited to being completely identical and may vary slightly depending on the heat and pressure conditions during transfer, but the visibility and texture of the matte effect, and the "rough tactile feel" of an Spc greater than 4000 mm-1 and an Rsm of 30 μm or more are maintained.

[0021] The surface shape of the transfer layer is ISO25178 The Spc (arithmetic mean curvature of the apex of the protrusion) specified in -1 The surface roughness must be greater than 100 μm, and the Rsm (average length of curved elements) as defined in JIS B0601:2013 must be 30 μm or greater. By having such a surface shape of the transfer layer, the transfer sheet of this embodiment can impart excellent matte visibility and texture (hereinafter, these may be collectively referred to as the "matte effect") to the adherend, and can also impart a particularly "rough" tactile feel to the adherend. The "rough" tactile feel is a sensual expression, but "rough" in this specification encompasses all tactile feels that are generally perceived as "rough." Specifically, it refers to the tactile feel felt when touching a rough surface with the pad of a finger, and can be described as a tactile feel that is not rough and smooth, but rather feels rough and rough. Examples of materials that have a "rough" feel include coarse cotton fabrics such as Oxford cloth made with thick threads of about 10 to 50 count (thick to medium count), and linen fabrics made with thick threads of about 10 to 50 count.

[0022] (Spc (arithmetic mean curvature of the apex of the protrusion)) Spc (arithmetic mean curvature of the apex of the protrusion) is ISO25178 It is one of the three-dimensional surface texture parameters defined in the standard, and is the average curvature (average sharpness) of the tip of the peak, calculated from the arithmetic mean value of the curvature radius of the peak (peak of the protrusion) of the part classified as a peak (convex part) in the feature image included in the reference area. Therefore, Spc is the reciprocal of the radius (mm) -1 )

[0023] The larger the Spc value, the greater the curvature of the tip of the peak (protrusion) (1a in Figure 1) (the reciprocal of the curvature radius is smaller, and the shape of the tip is sharper). On the other hand, the smaller the Spc value, the smaller the curvature of the apex of the protrusion (1b in Figure 1) (the reciprocal of the curvature radius is larger, and the shape of the tip is blunter). In other words, the smaller the Spc value, the more rounded the protrusion is, and the closer it is to a flat surface, the greater the gloss. For this reason, to suppress gloss by focusing only on the Spc value, it is necessary to use a surface shape with a large Spc (a surface shape with a sharp protrusion apex), i.e., 4000mm -1 Larger planar shapes result in increased light scattering at the surface, reducing gloss.

[0024] A surface shape with a small Spc value has rounded protrusions, making it soft to the touch. However, a large value, i.e., 4000mm -1 If the radius of curvature is larger (less than 0.25 mm), the sharp tip shape can be felt with a moderate contact frequency when touched with the pad of a finger, and this is thought to lead to the tactile sensation felt when touching a rough surface with the pad of a finger, which is not a soft sensation but a rough and rough sensation, i.e., a "rough" sensation. However, if the average spacing between the apexes of such sharp protrusions is too close, the existence of each sharp tip shape falls below the threshold of the resolution of the tactile sensation of the pad of a finger, and the sharp sensation of each protrusion is lost, resulting in a smooth and soft sensation. Therefore, the surface shape of a matte article is such that Spc>4000 mm -1 In addition to the above requirement, as will be described later, the requirement that Rsm (average length of curved elements) ≥ 30 μm, which corresponds to the average projection spacing, must also be satisfied.

[0025] In relation to the Rsm (average length of curved elements) described later, Spc is preferably 4200 mm from the viewpoint of improving the matte effect and rough touch. -1 More than 4250mm, preferably -1 More preferably, 4300 mm -1 The upper limit is preferably 7000 mm -1 less than 5000 mm, preferably -1 Less than or equal to 4500mm, preferably -1 Less than 4200mm, even more preferably -1 In the measurement of Spc in this specification, the cut-off value is 0.8 mm.

[0026] The Spc is measured using a shape analysis laser microscope on a rectangular area (1024 μm × 768 μm) at any location on the surface of the transfer layer. The measurement conditions can be adjusted as appropriate, and for example, measurements can be performed under the conditions described in the Examples. Furthermore, Rsm (average length of curved elements), Rz (maximum height), and Ra (arithmetic mean roughness), which will be described later, can also be measured in the same way.

[0027] (Rsm (average length of curved elements)) Among the three-dimensional surface texture parameters specified in JIS B0601:2013, Rsm (the average length of the curved element) is a horizontal parameter of the profile curve and is the average length of the profile element over a reference length. The larger the Rsm, the fewer the convex portions (2a and 2b in Figure 2) included in the reference length. Therefore, a surface shape with a large Rsm has sparsely spaced peaks of convex portions. By scattering the convex portions, i.e., by setting the peaks to 30 μm or greater, a sharp tip shape can be felt with a moderate contact frequency when touching with the pad of a finger. This is thought to lead to the tactile sensation felt when touching a rough surface with the pad of a finger, which is not soft but rather feels rough and rough, i.e., a "rough" tactile sensation. Furthermore, the relatively concave portions are thought to provide a matte effect.

[0028] Furthermore, if Rsm is reduced, the number of convex portions included within the reference length increases. This results in the formation of many convex portions on the surface, requiring a precise manufacturing process. For this reason, setting Rsm to 30 μm or more makes it possible to simplify the manufacturing process.

[0029] In this embodiment, by increasing Spc, it is possible to obtain a "rough" touch feeling while improving the matte effect. However, even if Spc is large, if Rsm is small, the apexes of the protrusions are densely present, and when the surface is stroked with a finger, the contact area with the finger becomes large, resulting in a soft touch feeling. For this reason, when Spc (arithmetic mean curvature of the apexes of the protrusions) is set to 4000 mm -1 It is believed that by making it larger and setting the Rsm (average length of the curved elements) to 30 μm or more, it has become possible to achieve both a matte effect and a "rough" tactile feel at a high level.

[0030] In relation to the Spc, from the viewpoint of improving the matte effect and the "rough" feel, the lower limit of Rsm is preferably 32.0 μm or more, more preferably 35.0 μm or more, and even more preferably 37.5 μm or more, and the upper limit is preferably 60.0 μm or less, more preferably 50.0 μm or less, and even more preferably 40.0 μm or less. By setting the upper limit within the above range, the planar shape exhibits a "rough" feel, and manufacturing is also preferable without becoming excessively difficult. In addition, when measuring Rsm in this specification, the cutoff value is 0.8 mm.

[0031] (Wrinkles) The surface shape of the transfer layer of this embodiment preferably has minute wrinkles (wrinkles) visible in a plan view as shown in FIG. 4 (described later). These wrinkles preferably have an irregular, uneven shape. Regarding the surface shape of the transfer layer of this embodiment, Spc (arithmetic mean curvature of the apex of the protrusions) and Rsm (average length of the curved elements), and preferably Rz (maximum height) and Ra (arithmetic mean roughness), described later, are likely to fall within specific numerical ranges due to the presence of these minute wrinkles (wrinkles). On the other hand, these minute wrinkles (wrinkles) are more likely to be formed by having Spc (arithmetic mean curvature of the apex of the protrusions) and Rsm (average length of the curved elements), and preferably Rz (maximum height) and Ra (arithmetic mean roughness), within specific numerical ranges. Thus, Spc (arithmetic mean curvature of the apex of the protrusions) and Rsm (average length of the curved elements), and the like, and minute wrinkles (wrinkles) can be said to be two sides of the same coin. Such a surface shape provides a "rough" feel to the touch and improves the matte effect.

[0032] (Rz (maximum height)) In this embodiment, the surface shape of the transfer layer preferably has a Rz (maximum height), which is a parameter in the horizontal direction of the profile curve defined in JIS B0601:2013, of 8.00 μm or more and 30.00 μm or less. Rz (maximum height) is one of the parameters for the peak and height of a profile curve, and is the sum of the height of the highest peak and the depth of the deepest valley within the profile curve over a reference length. The larger the Rz (maximum height), the more likely the convex portions are large (high) in shape relative to the valleys (depressions), and the greater the tendency for such convex portions to be present. Therefore, for a surface shape that satisfies the Spc (arithmetic mean curvature of the peaks of the protrusions) and Rsm (average length of the curved elements), if the Rz (maximum height) is 8.00 μm or more and 30.00 μm or less, the sharp tip shape of the convex portions as defined by the Spc (arithmetic mean curvature of the peaks of the protrusions) and Rsm (average length of the curved elements) is emphasized, improving the rough tactile feel. This also improves the matte effect.

[0033] From the viewpoint of improving the matte effect and the rough texture, Rz (maximum height) is preferably 8.50 μm or more, more preferably 9.00 μm or more, and even more preferably 9.50 μm or more, and the upper limit is preferably 26.00 μm or less, more preferably 24.00 μm or less, and even more preferably 22.00 μm or less. In the measurement of Rz (maximum height) in this specification, the cutoff value is 0.8 mm.

[0034] (Ra (arithmetic mean roughness)) In this embodiment, the surface shape of the transfer layer preferably has Ra (arithmetic mean roughness), which is a parameter in the horizontal direction of a profile curve defined in JIS B0601:2013, of 1.00 μm or more and 5.50 μm or less. Ra (arithmetic mean roughness) is a parameter of the height direction of a profile curve and is the average height difference from the mean plane of the profile curve over a reference length. The smaller the Ra (arithmetic mean roughness), the smaller the height difference of the convex portions and the corresponding concave portions in the surface shape of the transfer layer, indicating a tendency for the shape to be smoother and more uniform. Therefore, in a transfer layer surface shape that satisfies the Spc (arithmetic mean curvature of the apex of the convex portions) and Rsm (average length of the curved elements), if Ra (arithmetic mean roughness) is 1.00 μm or more and 5.50 μm or less, the convex portions of the surface shape of the transfer layer will have a more uniform and gentler shape, thereby reducing the tactile sensation, particularly improving the roughness of the texture. The matte effect is also improved.

[0035] From the viewpoint of improving the matte effect and the rough feel, Ra (arithmetic mean roughness) is preferably 5.25 μm or less, more preferably 5.00 μm or less, and even more preferably 4.50 μm or less, and the lower limit is preferably 1.00 μm or more, more preferably 1.50 μm or more, and even more preferably 1.75 μm or more. In measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

[0036] (Surface shape of transfer layer) The surface shape of the transfer layer of this embodiment preferably has wrinkles. As described above, stable formation of wrinkles on the surface of the transfer layer results in a layer that exhibits a stable matte effect due to the light diffusion effect caused by the wrinkle shape, and also exhibits a rough texture. Figure 4 is a schematic diagram of a plan view showing one embodiment of the transfer sheet of this embodiment, and is a schematic image of the surface of the transfer layer side of the decorative material obtained in the examples. Figure 4 shows that wrinkles are formed on the surface of the transfer layer of this embodiment. Here, "plan view" means viewing the surface of the transfer layer from the positive Z-axis direction in the XYZ coordinate system shown in Figures 3, 5, and 6.

[0037] The wrinkles that appear on at least one surface of the transfer layer are not particularly limited as long as they have the above-mentioned surface shape, i.e., a surface shape having Spc and Rsm within the above-mentioned specific numerical ranges, and preferably other Rz and Ra within the above-mentioned specific numerical ranges, and since the appearance of wrinkles results in the above-mentioned surface shape, a stable matte effect is exhibited and a rough texture is also exhibited. Regarding wrinkles, from the viewpoint of realizing the surface shape, improving the matte effect, and enhancing the rough feel, it is preferable that at least one surface of the transfer layer has an uneven shape constituted by irregular wrinkles, and the irregular wrinkles are preferably constituted by a plurality of convex portions formed by a plurality of protrusions and concave portions 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 for 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.

[0038] An example of the wrinkles is shown in Figure 4. Figure 4 shows that the surface of the transfer layer has irregular wrinkles in a planar view, and that the irregular wrinkles are configured to include a plurality of convex portions 2 formed by a plurality of curved linear protrusions and a concave portion 3 formed by being surrounded by the plurality of protrusions (a plurality of convex portions 2). It also shows that at least a portion of the curved convex portions 2 are each formed by a meandering linear protrusion, and that the meandering concave portion 3 is formed so as to be surrounded by the meandering linear protrusion. The transfer layer constituting the transfer sheet of this embodiment stably exhibits a matte effect and also exhibits a rough texture due to the stable formation of wrinkles as shown in Figure 4.

[0039] Here, "curved" means that there is one or more portions where the extension direction of the continuous linear protrusions 2 reverses from one side to the other in a planar view. Examples of portions where the extension direction reverses from one side to the other include a form having an inflection point when the linear protrusions 2 are approximated by a continuous curve when the width of the planar view shape is ignored (when the width is considered to be 0). Further examples include a form having a portion that is approximated by a V-shaped folded line or two sides of a triangle sandwiching one vertex when the linear protrusions 2 are approximated by a straight line when the width of the planar view shape is ignored.

[0040] Furthermore, "meandering" means that there are at least two or more portions where the extension direction of the continuous linear protrusions 2 reverses from one side to the other in a planar view (hereinafter also referred to as "reversed portions"). When the linear protrusions 2 proceed in their extension direction, the extension direction of the linear protrusions 2 alternately reverses in opposite directions at two adjacent portions. For example, when the width of the planar view shape of the linear protrusions 2 is ignored and the linear protrusions 2 are approximated by a continuous curve, an example of such a shape is one having a portion that can be approximated by the Roman letter "S." Furthermore, when the width of the planar view shape of the linear protrusions 2 is ignored and the linear protrusions 2 are approximated by a straight line, an example of such a shape is one having a portion that can be approximated by the Roman letter "W."

[0041] In this specification, "irregular" means a shape that does not have a fixed rule or is not arranged according to a fixed rule, i.e., is not patterned. A typical example of a non-irregular shape (regular shape) is a shape that is arranged with a fixed 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 their longitudinal direction. Therefore, the irregular wrinkles in this embodiment include a shape in which the shape of a single protrusion itself is irregular and not formed according to a fixed rule such as periodicity, a shape in which the shapes of multiple convex portions formed by multiple protrusions are irregular and not formed and arranged according to a fixed rule, and a shape in which a concave portion surrounded by such multiple protrusions is also irregular.

[0042] In the transfer layer constituting the transfer sheet of this embodiment, if any of the shape of a single protrusion (a single convex portion), the shape and arrangement of each of the multiple protrusions (multiple convex portions), and the shape of the recess surrounded by the multiple protrusions is irregular, a matte effect and a rough texture can be obtained due to the irregular wrinkles, but it is preferable that all of them are irregular.By having irregular wrinkles on the surface of the transfer layer, the transfer sheet of this embodiment improves the visibility and texture of the matte effect, and stably exhibits an extremely excellent matte effect and exhibits a rough texture.

[0043] As described above, the transfer layer has wrinkles, i.e., an uneven shape, on at least one surface thereof. The convex and concave portions in the uneven shape can be distinguished by, for example, utilizing the brightness difference of an image of the surface of the transfer layer of this embodiment, binarizing the image by assigning the darkest portion of the density distribution image a gradation of 255 and the lightest portion of the density distribution image a gradation of 0, with gradations of 0 to 255 representing concave portions in gradations of 0 to 127 and convex portions in gradations of 128 to 255. The image can be captured after the transfer layer is transferred to the adherend.

[0044] In this embodiment, the surface of the transfer layer preferably has irregular wrinkles formed on at least a portion thereof, and more preferably has irregular wrinkles formed over the entire surface. The location where the wrinkles are formed is not particularly limited as long as it is on the surface of the transfer layer, and is not limited to, for example, only locations corresponding to a pattern (on the pattern) described below, but the matte effect and rough texture due to the formation of wrinkles are realized as long as it is on at least a portion of the surface of the transfer layer. For example, if the product has a decorative layer as described below and irregular wrinkles are formed in some areas, forming the wrinkles in areas that correspond to the pattern on the decorative layer (for example, on the pattern) will make the pattern appear more matte than the surrounding area, thereby improving the design.

[0045] As shown in Figure 4, it is also preferable to have a plurality of convex portions formed by a plurality of protrusions that are irregular but have a certain degree of uniformity, and a concave portion surrounded by the convex portions. Therefore, a shape of one convex portion (protrusion portion) in which the width changes drastically is unlikely to achieve the above-mentioned surface shape, and is not a preferred embodiment for achieving the visibility and texture of the matte effect, nor is it a preferred embodiment for achieving a rough tactile feel. Specific embodiments of the shapes of the convex portions (protrusion portions) and concave portions that form irregular wrinkles, which can be advantageous in stably improving the matte effect and improving the rough tactile feel, are described below. When the wrinkles have the following shape, the above-mentioned surface shape is easily achieved, and the matte effect and rough tactile feel are improved.

[0046] Regarding the shape of the wrinkles formed on at least one surface of the transfer layer, the height of the convex portions (height of the protrusions) is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of about 10 μm or less. Furthermore, the width of the convex portions is preferably 0.1 μm or more, more preferably 0.3 μm or more, and even more preferably 0.5 μm or more, with an upper limit of 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 portions are within the above ranges, the surface shape is easily achieved, and in relation to the concave portions, the matte effect is stably improved and the rough texture is improved.

[0047] Here, the dimensions of the convex portions are the average values ​​of 10 convex portions (protrusions) at 10 arbitrary locations (100 μm square area × 10 locations) on the transfer sheet of this embodiment, i.e., a total of 100 convex portions. Also, as shown in FIG. 3, the width of each convex portion (protrusion) is not uniform but varies, so the width of one convex portion (protrusion) is the average value of the widths at five arbitrary locations on that one convex portion (protrusion). The same applies to the height of the convex portions (protrusions).

[0048] The depth of the recesses is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, with an upper limit of about 10 μm or less. The width of the recesses is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, with an upper limit of 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 recesses are within the above ranges, the surface shape is easily achieved, and in relation to the protrusions, the matte effect is stably improved and the rough texture is improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0049] 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, with the upper limit being 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 surface shape is easily exhibited, the matte effect is stably improved, and the rough texture is improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0050] The proportion of the convex portions is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, with the upper limit being preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. When the proportion of the convex portions is within the above range, the surface shape is easily achieved, and in relation to the proportion of the concave portions surrounded by the convex portions, the matte effect is stably improved and the rough texture is improved. Here, the occupancy ratio of the convex portions is the average value of the occupancy ratio of the convex portions at any 10 locations (100 μm square area×10 locations) on the transfer sheet of this embodiment.

[0051] The convex portions and concave portions may have portions of approximately the same direction and width, but from the viewpoint of improving the matte effect and the rough texture, it is preferable that the length be short. Specifically, the length of the continuous convex portions and concave portions of approximately the same direction and width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, with the lower limit being preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, thereby stably improving the matte effect and improving the rough texture. Here, of any 10 convex portions and concave portions (i.e., a total of 100 convex portions and concave portions) in any 10 locations (100 μm square areas × 10 locations) on 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. Furthermore, in this specification, the "substantially the same" in "substantially the same" means roughly the same, without branching, meaning a difference of ±3° in the direction, and a difference of ±5% in the width.

[0052] The number of convex portions (projections) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, with the upper limit being preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. When the number of convex portions is within the above range, the matte effect is stably improved and the rough texture is also improved. The number of convex portions is the average value of the number of convex portions in 10 locations (100 μm square area×10 locations) on the transfer sheet of this embodiment.

[0053] FIG. 5 is a cross-sectional view showing one embodiment of the transfer layer 20 constituting the transfer sheet of this embodiment, in which the transfer layer is cut along a plane parallel to its thickness direction (Z direction in the figure). The shape of the recess may be, for example, acute-angled as shown in 3a in Figure 5, semicircular or semi-elliptical as shown in 3b, or a combination of these.Furthermore, a shape such as 3c in Figure 5, in which one protrusion has a recess in a part thereof, may also be used. On the other hand, the shape of the convex portion is semicircular or semielliptical, although the width varies as shown in 2c and 2d of FIG.

[0054] (Formation of the surface shape of the transfer layer) The surface shape of the transfer layer is preferably formed based on the surface shape of the basic matte layer described below. By first preparing the basic matte layer and then forming the surface of the transfer layer, the desired surface shape can be formed without the inclusion of wrinkle formation stabilizers, etc. In other words, the transfer layer does not need to contain wrinkle formation stabilizers, etc., which are necessary for forming the basic matte layer described below. Furthermore, the resin constituting the transfer layer is different from that of the basic matte layer, providing more options. By preparing the basic matte layer in this manner, the transfer layer can be made into a resin composition that improves weather resistance by adding ultraviolet absorbers, radical scavengers, etc., which is preferable.

[0055] Regarding the surface shape of the transfer layer, it is preferable to design the surface shape of the releasable support so that Spc (arithmetic mean curvature of the apex of the protrusions), Rsm (average length of the curved elements), Rz (maximum height), and Ra (arithmetic mean roughness) satisfy preferred ranges. This is because the surface structure of the transfer layer will have a shape that reflects the surface shape of the releasable support. Of the above parameters, the value of Spc is preferably adjusted to the shape of the recesses of the releasable support, since the shape of the recesses of the releasable support becomes the shape of the protrusions of the transfer layer.

[0056] A method for adjusting the shape of the recesses in the releasable support will be described. When the surface shape A of the article is inverted once, it becomes a surface shape complementary to the shape A. Then, when the complementary surface shape is inverted again, it returns to the same surface shape as the surface shape A. (The term "same" as used above does not necessarily mean completely identical, but means identical with a degree of tolerance that allows for the Spc and Rsm to fall within specific ranges, so that the visibility of the matte effect, the texture, and the rough tactile feel of the initial surface shape are maintained.) In other words, when the surface shape of the article is inverted twice, it returns to the original surface shape. This double inversion can be used to adjust the convex shape of the surface shape of the transfer layer. For this reason, it is preferable to first prepare a basic matte layer (hereinafter also referred to as "basic matte layer"), and then form the surface shape of the release support into a shape that is the inverse of the surface shape of the basic matte layer.Release supports having a surface shape that is the inverse of the surface shape of the basic matte layer can be produced, for example, by the following three methods (1-1) to (1-2), (2-1) to (2-3), and (3-1) to (3-2).

[0057] (1-1) A basic matte layer A is prepared that satisfies parameters such as Spc and Rsm. (1-2) The basic matte layer A is pressed against the surface of a releasable support, and the surface of the releasable support is molded into a shape that is an inverse of the surface shape of the basic matte layer A. The basic matte layer A corresponds to the basic matte layer described below. As the release support, a laminate having a release layer on a support is preferably used, and when the basic matte layer A is pressed against the surface of the release layer, the release layer is left in an uncured state, and then cured, so that the surface of the release layer (= the surface of the release support) can be molded into a shape that is the inverse of the surface shape of the basic matte layer A.

[0058] (2-1) A basic matte layer A is prepared that satisfies parameters such as Spc and Rsm. (2-2) Mold A is prepared with the same surface shape as the basic matte layer A. Mold A with the same surface shape as the basic matte layer A can be obtained, for example, by preparing mold B with the inverted surface shape of the basic matte layer A, and then preparing a mold with the inverted surface shape of mold B. The mold with the inverted surface shape of mold B is mold A. Molds A and B can be prepared by a general-purpose mold preparation method such as electroforming.

[0059] (2-3) Mold A is pressed against the surface of a releasable support, and a shape that is the inverse of the surface shape of mold A (= the surface shape of basic matte layer A) is imprinted on the surface of the releasable support. As the releasable support, a laminate having a release layer on a support is preferably used, and when mold A is pressed against the surface of the release layer, the release layer is left in an uncured state, and then cured, so that a shape that is the inverse of the surface shape of mold A (= the surface shape of basic matte layer A) can be imprinted on the surface of the release layer (= the surface of the releasable support).

[0060] (3-1) A surface shape that satisfies parameters such as Spc and Rsm is designed through simulation, and mold C is fabricated by reproducing the designed surface shape through laser micromachining. (3-2) Mold C is pressed against the surface of a releasable support, and a shape that is the inverse of the surface shape of mold C (= a surface shape that satisfies parameters such as Spc and Rsm) is imprinted on the surface of the releasable support. As the releasable support, a laminate having a release layer on a support is preferably used, and when mold C is pressed against the surface of the release layer, the release layer is left in an uncured state, and then cured, so that a shape that is the inverse of the surface shape of mold C (= a surface shape that satisfies parameters such as Spc and Rsm) can be imprinted on the surface of the release layer (= the surface of the releasable support). As the above (3-1), the surface shape to be molded by the mold C of the above (3-2) may be designed by simulation, and a mold C' that reproduces the designed surface shape by laser micromachining may be produced, and used as a releasable support to mold an inverted shape.

[0061] The thickness of the basic matte layer is not particularly limited as long as it is a thickness that can stably exhibit a matte effect and can form the above-mentioned wrinkles to the extent that a rough feel can be exhibited. However, 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 still 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 still more preferably 100 μm or less.

[0062] In this specification, the thickness of the matte layer is determined by measuring the thickness at 20 points on an image of the cross section of the transfer sheet taken using a scanning electron microscope (SEM), and averaging the values ​​at 20 points. The acceleration voltage of the SEM is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[0063] The basic matte layer is a layer that exhibits the above-mentioned surface shape over its entire surface, and since the transfer layer of this embodiment has a surface shape over at least a part of its surface, it is sufficient that it is provided on at least a part of the surface of the transfer layer, and it may be provided over the entire surface. When the transfer layer of this embodiment has the release layer, it is sufficient that it is provided on at least a part of the surface of the release layer, and it may be provided over the entire surface. As long as the matte layer is provided in a location on the transfer layer that is visible and touched by the consumer, i.e., as long as the surface shape is provided in a location on the cosmetic material that is visible and touched by the consumer, the effects of the invention, namely, the matte effect and rough texture, will be obtained.

[0064] Furthermore, even when the substrate is in the form of a film, sheet, or plate, the basic matte layer only needs to be provided in a location in the decorative material that is visible and touched by the consumer, and only needs to be provided on at least a portion of one of its surfaces, or it may be provided on the entire surface, and from the viewpoint of improving the matte effect and the rough tactile feel, it is preferable that it be provided over the entire surface of one of its surfaces, as shown in Figures 3, 5, and 6.

[0065] (basic matte layer) Regarding the manufacturing methods (1-1) to (1-2) and (2-1) to (2-3), the basic matte layer used in "preparing the recessed shape of the release support" is (1) Forming a fine wrinkle structure on the surface of the basic matte layer, It is preferable. Furthermore, the basic matte layer is (2) The composition of the resin composition for forming the basic matte layer, in particular the type of polymerizable monomer and polymerizable oligomer, the number of functional groups, the molecular weight, the presence or absence of a wrinkle formation stabilizer, and if a wrinkle formation stabilizer is used, the particle size and content of the wrinkle formation stabilizer are optimized. (3) Optimizing the irradiation conditions of the resin composition for forming the basic matte finish, particularly the wavelength of light having a wavelength of 100 nm or more and 380 nm or less that can cure and shrink the surface portion of the basic matte finish layer, the cumulative weight, the ultraviolet output density, etc. (4) In addition to the above, the type and thickness of the substrate on which the basic matte layer is formed, the thickness of the basic matte layer, etc. are optimized. It is preferable. By optimizing these, it becomes easier to keep the Spc (arithmetic mean curvature of the apex of the protrusion) and Rsm (average length of the curved element) of the surface shape of the basic matte layer (= the surface shape of the transfer layer in this embodiment) within the specific numerical ranges, and preferably to keep the Rz (maximum height) and Ra (arithmetic mean roughness) described below within the specified numerical ranges.

[0066] The basic matte layer is preferably a layer constituted by a cured product of a resin composition, preferably a cured product of a curable resin composition containing a cured resin.

[0067] The resin composition for forming the basic matte layer is preferably a resin composition containing a resin and a wrinkle formation stabilizer (hereinafter, sometimes referred to as a "resin composition for forming the basic matte layer"), from the viewpoint of obtaining a basic matte layer having an excellent matte effect and an excellent rough feel. That is, the basic matte layer is preferably a layer containing a resin and a wrinkle formation stabilizer.

[0068] (Wrinkle formation stabilizer) The wrinkle formation stabilizer stabilizes wrinkle formation on at least one surface of the basic matte layer, thereby achieving uniform visibility of the matte effect across the entire surface of the basic matte layer and reducing localized unevenness in gloss, thereby imparting stable visibility of the matte effect (hereinafter, simply referred to as "stable visibility of the matte effect" or equivalent expressions) and uniformity of the surface condition (also referred to as "texture"). Furthermore, wrinkles formed in the basic matte layer directly become wrinkles in the transfer layer (peeling layer), which significantly contributes to the development of a rough texture in the transfer sheet. In other words, the improvement in the visibility, texture, and rough texture of the matte effect of the basic matte layer described below also significantly contributes to the development of the visibility, texture, and rough texture of the matte effect that can be imparted by the transfer sheet of this embodiment.

[0069] Therefore, even if the so-called "matting agent" in the prior art and the "wrinkle formation stabilizer" in the present embodiment have the same constituent substances and average particle diameter, they differ in the matting mechanism (action), the structure for realizing the matte finish, the amount used, and the relationship between the surface gloss (gloss value). Furthermore, they differ from "matting agents" in that they create a rough texture by forming wrinkles.

[0070] In the prior art such as Patent Document 1, matting agents used to achieve a matte finish themselves exhibit a visible matte finish due to a light diffusion effect resulting from their physical shape. Specifically, what is generally referred to as a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and exhibits a visible matte finish due to a light diffusion effect at the interface where light reflects and refracts corresponding to the particle's contour shape. On the other hand, the wrinkle formation stabilizer of the present embodiment does not exhibit a visible matte finish due to light diffusion caused by the reflection and refraction of light by the particles themselves, but stabilizes the formation of wrinkles on the surface of the matte layer due to the wrinkle formation stabilizer, thereby imparting a stable matte finish and texture to the matte layer due to a light diffusion effect at the interface where the refractive index difference between the surface and air occurs. 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 both are the same).

[0071] Furthermore, the relationship between the content of a "wrinkle formation stabilizer" and a "matt agent" also differs in terms of the surface gloss (gloss value). When the same substance A is used as a wrinkle formation initiator AW (W: wrinkle), 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 and is contained in the specific amount C but no wrinkles are formed on the surface. 60° AM (C) is clearly lower than (C). In other words, the following relationship holds: G 60° AW (C) <G 60° AM (C)

[0072] The release layer may contain an agent conventionally used as a matting agent, but preferably does not contain a matting agent. Thus, the release layer of this embodiment can be said to have extremely excellent visibility and texture of the matte effect, even if it does not substantially contain a matting agent conventionally used to obtain visibility of the matte effect. Here, "not containing a matting agent" means that not only does it not contain any matting agent, but also that even if it does contain one, the matte effect due to the action and effect of the matting agent itself is not visible. Specifically, the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, and more preferably 3.0 parts by mass or less, per 100 parts by mass of the resin. In this specification, the term "matting 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 matting agent can be contained, i.e., more than 30 μm, from the viewpoint of forming convex portions by the head-exposing effect as described above.

[0073] Any wrinkle formation stabilizer can be used without particular limitation as long as it is not a matting agent and has an average particle size of 100% or less of the thickness of the basic matte layer or 30 μm or less, whichever is smaller. From the viewpoint of improving the matte effect and the rough texture, it is preferable to use at least one of two types of wrinkle formation stabilizers distinguished by their average particle diameters for the wrinkle formation stabilizer having an upper limit of the smaller of 100% or less of the thickness of the basic matte layer or 30 μm or less. Specifically, the two types of wrinkle formation stabilizers are Wrinkle Formation Stabilizer 1, which has an average particle diameter of 1 μm or more and an upper limit of the smaller of 100% or less of the thickness of the matte layer or 30 μm or less, and Wrinkle Formation Stabilizer 2, which has an average particle diameter of less than 1 μm. In this embodiment, the use of at least one of the two types of wrinkle formation stabilizers stabilizes wrinkle formation, provides a stable and excellent matte effect, and also provides a rough texture. In this embodiment, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used alone, or wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used in combination. From the viewpoint of improving the matte effect and rough texture, wrinkle formation stabilizer 1 is preferred, and wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can also be used in combination.

[0074] As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of organic materials that can be used to form 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, and among these, silica is preferred because of its excellent transparency.

[0075] The shape of the wrinkle formation stabilizer is not particularly limited, but examples thereof include spherical, polyhedral, scaly, and amorphous shapes.

[0076] The average particle size of the wrinkle formation stabilizer 1 is 1 μm or more, and the upper limit is the smaller of 100% or less of the thickness of the basic matte layer or 30 μm or less. From the viewpoint of stably improving the matte effect and improving the rough tactile feel, the average particle size of the 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. The upper limit, relative to the thickness of the basic matte layer, is preferably 90% or less of the thickness of the basic matte layer, more preferably 80% or less of the thickness of the basic matte layer, and even more preferably 70% or less of the thickness of the basic matte layer. 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. Any combination of the upper limit relative to the thickness of the basic matte layer and the upper limit of the absolute value may be used, whichever is smaller. For example, the upper limit may be the smaller of 90% or less of the thickness of the basic matte layer or 20 μm or less, or the smaller of 90% or less of the thickness of the basic matte layer or 10 μm or less. The thickness of the basic matte layer will be described later.

[0077] The average particle size of the wrinkle formation stabilizer 2 is less than 1 μm. From the viewpoints of stabilizing wrinkle formation, stably improving the matte effect, and improving the rough feel to the touch, the average particle size 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 laser light diffraction method.

[0078] From the viewpoint of stabilizing wrinkle formation by the wrinkle formation stabilizer, stably improving the matte effect, and improving the rough texture, the content of the wrinkle formation stabilizer (when wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 are used in combination, the total content of these) is basically preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, even more preferably 1.0 part by mass or more, and still more preferably 1.2 parts by mass or more, relative to 100 parts by mass of the resin that forms the matte layer. There is no particular upper limit from the viewpoint of improving the stable matte effect and the rough texture, but from the viewpoint of, for example, improving the productivity of the cosmetic material due to the coatability of the resin composition for forming the basic matte layer, and efficiently improving the visibility and texture of the matte effect, the content is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, even more preferably 10.0 parts by mass or less, still more preferably 7.5 parts by mass or less, and particularly preferably 6.0 parts by mass or less.

[0079] When wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 are used in combination, the contents of each of them are not particularly limited as long as the total content is within the above-mentioned range, but the content of wrinkle formation stabilizer 2 is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and even more preferably at least 1.0 part by mass, relative to 100 parts by mass of resin, and preferably at most 10.0 parts by mass, more preferably at most 7.5 parts by mass, even more preferably at most 5.0 parts by mass, and even more preferably at most 3.5 parts by mass. Furthermore, the blending ratio of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, relative to 100 parts by mass of the total amount of these, is preferably 0.05 to 0.95 parts by mass, more preferably 0.10 to 0.90 parts by mass, even more preferably 0.20 to 0.80 parts by mass, and even more preferably 0.30 to 0.70 parts by mass.

[0080] As described above, organic particles and inorganic particles can be used as wrinkle formation stabilizers, but these particle types themselves can also be said to include those conventionally used as matting agents. For example, matting agents such as spherical alumina and calcium carbonate are used in the matte layer of the decorative sheet described in Patent Document 1. In order for matting agents such as spherical alumina and calcium carbonate to exhibit the visibility of their matting effect due to the light diffusion effect caused by their physical shape, they need to be used in a total content of about 50 parts by weight, consisting of 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of resin, as described in Patent Document 1. However, in the present embodiment, even at a small content as described above, i.e., a content less than the content required to exhibit the visibility of the matting effect due to the light diffusion effect caused by the physical shape, an extremely superior matting effect compared to the effect obtained by a matting agent is obtained, and a rough tactile feel is also obtained. Therefore, it can be said that the matte layer of this embodiment, although it does not substantially contain a matting agent, stably forms wrinkles on the surface, thereby stably providing a superior matte effect visibility compared to when a matting agent is used, while also providing a texture and even a rough feel to the touch.

[0081] (resin) The resin forming the basic matte layer may be any resin that can be formed by forming a resin composition for forming the basic matte layer containing a predetermined amount of the wrinkle formation stabilizer and curing it to form a cured product that forms the basic matte layer. Examples of such resins include ionizing radiation curable resins. As mentioned above, when the basic matte layer itself is used as a mold-transfer sheet (see 1-2 above), or when a mold is manufactured based on the basic matte layer (see 2-2 above). For this reason, it is preferable that the resin forming the matte layer be a resin that easily exhibits surface properties such as processing characteristics, and ionizing radiation curable resins are preferred from these perspectives. The basic matte layer maintains its matte effect and rough texture and can impart a desired shape to the transfer sheet, so that the desired shape can also be imparted to the decorative material obtained using the transfer sheet.

[0082] The ionizing radiation curable resin is a resin having an ionizing radiation curable functional group, which is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred 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 term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group. In this specification, the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet (UV) rays 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.

[0083] Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet curable resins, and ultraviolet curable resins are preferred from the viewpoint of stabilizing the formation of wrinkles by the wrinkle formation stabilizer, stably improving the matte effect, and improving the rough tactile feel. 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.

[0084] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferred, and among them, a polyfunctional (meth)acrylate monomer is preferred. Here, "(meth)acrylate" means "acrylate or methacrylate." Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group.

[0085] From the viewpoint of stabilizing wrinkle formation and stably improving the matte effect, improving the rough texture, and steadily imparting a shape having a matte effect and a rough texture to the transfer sheet, 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. Furthermore, with the above-mentioned number of functional groups, the above-mentioned surface shape is particularly easily obtained and the rough texture is easily improved. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0086] Examples of polymerizable oligomers 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.

[0087] Other polymerizable oligomers 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 chain, 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 molecule, such as novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0088] 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 matte effect, improving the rough texture, and reliably imparting a shape having a matte effect and a rough texture to a transfer sheet, 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, with urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers being more preferred, and urethane (meth)acrylate oligomers being even more preferred.

[0089] The number of functional groups of these polymerizable oligomers is determined from the viewpoints of stabilizing wrinkle formation and stably improving the matte effect, improving the rough texture, Furthermore, from the viewpoint of steadily imparting a matte effect and a texture with a rough feel to the transfer sheet, the number is preferably 2 or more and 8 or less, more preferably 6 or less, and even more preferably 4 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.

[0090] In this embodiment, the resin for forming the basic matte layer can be the polymerizable oligomer alone, the polymerizable monomer alone, or a combination of the polymerizable oligomer and the polymerizable monomer. However, from the viewpoint of stabilizing wrinkle formation and consistently improving the matte effect, improving the rough texture, and reliably imparting a matte effect and a rough texture to the transfer sheet, it is preferable to use the polymerizable monomer alone or a combination of the polymerizable oligomer and the polymerizable monomer. As the polymerizable oligomer, a polyfunctional urethane (meth)acrylate oligomer is preferred, and a polyfunctional urethane acrylate oligomer is more preferred. As the polymerizable monomer, a polyfunctional polymerizable monomer is preferred, and a polyfunctional (meth)acrylate monomer is more preferred, and a polyfunctional acrylate monomer is even more preferred.

[0091] When used in combination, from the same viewpoint, the content of the polymerizable oligomer relative to 100 parts by mass of the total 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.

[0092] (Resin composition) The basic matte layer is preferably composed of a cured resin composition containing the wrinkle formation stabilizer in a predetermined content, and the resin composition preferably contains the resin and the wrinkle formation stabilizer in a predetermined content. In addition to the wrinkle formation stabilizer and resin, the resin composition may contain other components depending on the desired performance, etc. The resin composition for forming the basic matte layer may contain a monofunctional (meth)acrylate, for example, for the purpose of reducing its viscosity, etc. These monofunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0093] Furthermore, when the resin is an ultraviolet-curable resin that is cured by ultraviolet light, it preferably contains additives such as a photopolymerization initiator, a photopolymerization accelerator, etc. By including these additives, the resin can be cured even with ultraviolet light (without ionizing radiation), and practical surface properties can be obtained.

[0094] The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil 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 rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0095] (Basic matte layer formation method) The method for forming the basic matte layer includes a basic matte layer forming step of irradiating a layer of a resin composition for forming the basic matte layer, which contains the resin and a wrinkle formation stabilizer, with light having a wavelength of at least 100 nm or more and 380 nm or less. This formation method can form a basic matte layer having a surface shape such as that shown in Fig. 5 (the transfer layer in Fig. 5 is obtained by inverting the surface shape of the basic matte layer twice. That is, the surface shape of the transfer layer in Fig. 5 is identical to the surface shape of the basic matte layer. "Identical" here has the same meaning as described above.) For example, a laminate having a substrate and a basic matte layer can be produced by applying the resin composition for forming the basic matte layer to a substrate, forming a layer of the resin composition on the substrate, and irradiating the substrate with light of the wavelength described above to form the basic matte layer. This forming method is suitable for forming a basic matte layer having a matte effect with a 60° gloss value of 20.0 or less, 10.0 or less, or even less than that, and having a rough feel to the touch.

[0096] In the case of a fibrous substrate such as paper, when a liquid matte layer-forming resin composition is applied, the liquid composition penetrates into the substrate, causing the unevenness of the fibers on the substrate surface to appear on the matte layer surface, which can prevent the desired Spc and Rsm values ​​from being obtained. In such cases, it is preferable to form a known permeation-blocking resin layer on the matte layer-forming surface of the fibrous substrate by a coating method or other method. Examples of resins for forming such permeation-blocking resin layers include two-component curing urethane resins.

[0097] This method for forming a matte layer makes it easy to obtain a basic matte layer. Specifically, in forming the basic matte layer, a resin composition for forming the matte layer, which contains a wrinkle formation stabilizer, is irradiated with ultraviolet light having a short wavelength of at least 100 nm or more and 380 nm or less, thereby forming wrinkles on at least one surface of the basic matte layer, thereby imparting a matte effect and a rough texture to the basic matte layer.

[0098] When such short-wavelength ultraviolet light is irradiated onto the resin composition for forming the matte layer, wrinkles are formed on at least one surface of the matte layer, basically resulting in the matte effect and a rough texture. Although the details of the mechanism by which this occurs are unknown, it is presumed to be due to the following mechanism.

[0099] When a coating layer formed by applying a resin composition for forming a basic matte layer to a predetermined thickness is irradiated with short-wavelength ultraviolet light, the energy of the ultraviolet light penetrates only the surface portion and does not reach the layers below, so that only the surface portion of the resin composition begins to harden, and as a result, only the surface undergoes cure shrinkage, resulting in the formation of wrinkles.In this way, it is thought that wrinkles are formed when the resin composition for forming the basic matte layer is cured only in a certain thickness direction from the surface due to irradiation with short-wavelength ultraviolet light.

[0100] Furthermore, a comparison between the Examples and Comparative Examples described below reveals that when a wrinkle formation stabilizer is not included, wrinkle formation becomes unstable, the visibility and texture of the matte effect are not stably and sufficiently exhibited over the entire surface of the basic matte layer, and the rough texture is not sufficiently exhibited, so the stable expression of the matte effect and rough texture cannot be explained by curing only the surface portion due to short-wavelength ultraviolet light. In other words, the inclusion of a wrinkle formation stabilizer is essential for the basic matte layer to have stable wrinkles and thereby exhibit the matte effect and rough texture. Considering that the stable matte effect and rough texture due to wrinkle formation are not obtained when the wrinkle formation stabilizer is not included, it is thought that the wrinkle formation stabilizer functions like a nucleus that triggers wrinkle formation, and the resin on the surface of the resin composition gathers around this nucleus, forming convex wrinkles (protrusions), and as the convex wrinkles (protrusions) form, concave wrinkles also form, resulting in stable wrinkle formation and a stable matte effect and rough texture.

[0101] In the method for forming the basic matte layer, the resin composition for forming the basic matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. As described above, this irradiation allows the ultraviolet energy to penetrate only the surface portion, preventing the energy from reaching the layers below. Therefore, only the surface portion of the resin composition begins to harden. This causes curing shrinkage only at the surface, stabilizing the formation of wrinkles. The surface layer of the resin composition then becomes a cured product, forming the basic matte layer. Subsequently, curing progresses from the surface-prone portion, where curing proceeds slowly, to the deeper portion, away from the surface. The resin composition layer then hardens, forming a cured product. This hardens throughout the entire thickness of the resin composition, and creates a light-diffusing effect on the surface, forming a wrinkled basic matte layer with a rough texture. To promote the progress of curing into the deeper portion, it is preferable to perform another irradiation treatment after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, as described below.

[0102] Examples of light with a wavelength of at least 100 nm or more and 380 nm or less include "excimer light," which includes light in the ultraviolet wavelength range from excited dimers formed by discharge of rare gases such as Ar, Kr, Xe, and Ne, halides of rare gases such as halogens F, Cl, I, and Br, or mixed gases thereof, i.e., excimers. Examples of wavelengths and excimer light sources that can be used include light with a wavelength of 126 nm emitted from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), and 351 nm (XeF). The excimer light can be either spontaneous emission light or laser light with high coherence due to stimulated emission, but spontaneous emission light is usually sufficient. Note that discharge lamps that emit this light (ultraviolet light) are also called "excimer lamps."

[0103] 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.). The use of such excimer light stabilizes wrinkle formation, improves the matte effect stably, and also improves the rough texture.

[0104] From the viewpoint of stabilizing wrinkle formation, stably improving the matte effect, and improving the rough texture, 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 preferably 320 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, still more preferably less than 200 nm, and most preferably 172 nm (Xe2). Thus, in this embodiment, from the viewpoint of stably improving the matte effect and improving the rough texture, it is preferable to use light with a shorter wavelength, and it can be said that medium-wavelength ultraviolet light (wavelength: 280 to 320 nm) or short-wavelength ultraviolet light (wavelength: 280 nm or less) is more preferable, and short-wavelength ultraviolet light is even more preferable. It is preferable that the short-wavelength ultraviolet light has a wavelength of less than 200 nm.

[0105] The integrated light amount of the wavelength light is preferably 1 mJ / cm from the viewpoint of stabilizing the formation of wrinkles, stably improving the matte effect, and improving the rough texture. 2 More preferably, 10 mJ / cm 2 More preferably, 30 mJ / cm 2 More preferably, 50 mJ / cm 2 There is no particular upper limit, 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 or less, more preferably 300 mJ / cm 2From the same viewpoint, the ultraviolet light output density is preferably 0.001 W / cm or more, more preferably 0.01 W / cm or more, and even more preferably 0.03 W / cm or more, with the upper limit being preferably 10 W / cm or less, more preferably 5 W / cm or less, and even more preferably 3 W / cm or less. Furthermore, the oxygen concentration during irradiation with light of the above wavelengths is preferably lower, 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.

[0106] In the basic matte layer forming step, in addition to the irradiation with light having a wavelength of at least 100 nm or more and 380 nm or less, other treatments that contribute to curing of the resin composition for forming the basic matte layer may be carried out. For example, to stabilize the formation of wrinkles due to the difference in the degree of curing between the surface portion and the deep portion away from the surface in the depth direction and to promote the curing progress to the deep portion, the resin composition for forming the basic matte layer may be pre-cured overall by pre-irradiation with light having a wavelength exceeding 380 nm, preferably light having a wavelength of 385 nm to 400 nm, and then irradiated with light having a wavelength of 100 nm to 380 nm. Alternatively, after irradiation with light having a wavelength of 100 nm to 380 nm, post-curing may be performed to further cure the resin composition. The necessity of pre-curing and post-curing can be determined appropriately depending on the desired properties of the basic matte layer (e.g., surface properties such as processing characteristics and stain resistance). Furthermore, although the above-mentioned wavelength light belongs to the ultraviolet ray family, other ionizing radiations, such as electron beams, can also be used. For example, electron beams are preferably used in post-curing to improve the surface properties of the basic matte layer.

[0107] In the method for forming the basic matte layer, the basic matte layer can be formed by applying a resin composition for forming the matte layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, to form a coated layer (uncured resin layer), and irradiating the coated layer with light having a wavelength of at least 100 nm or more and 380 nm or less.

[0108] <Releasable support> The release support is peeled off from the transfer layer after the transfer layer is transferred to the adherend. The surface shape of the release support is the inverse of the surface shape that the transfer sheet of this embodiment can impart to the adherend, i.e., the inverse of the surface shape of the transfer layer. Furthermore, as described above, the surface shape of the release support is preferably formed by a basic matte layer. The releasable support may have a single layer structure or a two or more layer structure, and is preferably configured to have a release layer on the support.

[0109] [Support] The material of the support is not particularly limited, and examples thereof include paper, fiber, metal, glass, ceramics, and resin. Among these, a support made of resin is preferred because it is easy to form a release layer and has good peeling workability after transfer. Hereinafter, a support made of resin will be referred to as a plastic sheet. Films, sheets, and plates are referred to as films, sheets, and plates in order of relative thickness, but there is no significance in strictly distinguishing between these three types in this specification, and differences between these three types do not cause any difference in interpretation of the rights of the present invention.

[0110] There is no particular limitation on the thickness of the support. That is, the support in this embodiment may be a support having a thickness on the order of micrometers, or a support having a thickness on the order of millimeters or more. The support may be colored or uncolored. When the support is colored, the coloring mode is not particularly limited, and the support may be transparently colored or opaquely colored (hiding colored).

[0111] Examples of resins that can be used to form plastic films include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins typified by nylon 6 or nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABS); polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins. Of these, polyester resins are preferred, and among polyester resins, polyethylene terephthalate is preferred.

[0112] The thickness of the plastic film is not particularly limited, but in order to improve the handleability of the transfer sheet, it is preferably 10 μm or more and 200 μm or less, more preferably 15 μm or more and 150 μm or less, and even more preferably 30 μm or more and 125 μm or less.

[0113] In order to enhance 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.

[0114] [Release layer] The release layer is a layer that is provided as needed to improve the releasability between the releasable support and the transfer layer, and to function as a "mold" for giving the transfer layer (release layer) a surface shape. The release layer is preferably provided over the entire surface of the support in order to improve the releasability from the transfer layer and to give a surface shape to the entire surface of the transfer layer (release layer). The release layer preferably contains a resin, and more preferably contains a resin and a release agent.

[0115] (resin) The release layer preferably contains a resin as its main component, which means that the resin accounts for 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, more preferably 90% by mass or more, and more preferably 95% by mass or more.

[0116] In order to improve durability, the release layer preferably contains, as the resin, a cured product of a resin composition containing a curable resin. The proportion of the cured resin composition containing the curable resin relative to the total amount of resin contained in the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 100% by mass.

[0117] 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 an ionizing radiation curable resin is preferred in that it is easier to improve scratch resistance.

[0118] A resin composition containing a thermosetting resin is a composition containing at least a thermosetting resin and is a resin composition that hardens when heated. Examples of thermosetting resins include acrylic resins, urethane resins, urethane acrylic resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. These can be used alone or in combination. Furthermore, a resin composition containing a thermosetting resin may contain a hardener such as an isocyanate-based hardener or an epoxy-based hardener.

[0119] As the ionizing radiation curable resin for the release layer, those exemplified as the ionizing radiation curable resin for the matte layer can be used.

[0120] (mold release agent) Examples of the release agent include fluorine-based release agents and silicone-based release agents, and silicone-based release agents are preferred from the viewpoint of obtaining lower cost and higher releasability.

[0121] Examples of silicone-based release agents include those having a polysiloxane structure as a basic structure. Among these, modified silicone oils having organic groups introduced into at least one of the side chains and terminals are preferred, and modified silicone oils having organic groups introduced into both terminals are more preferred. From the viewpoint of achieving a more sophisticated design, preferred organic groups 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 these, reactive functional groups are preferred, and (meth)acrylic groups are particularly preferred, i.e., (meth)acrylic-modified silicone oils are particularly preferred. Furthermore, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

[0122] 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, relative to 100 parts by mass of the resin that forms 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.

[0123] The surface shape of the release layer is an inverted shape of the surface shape of the transfer layer. Therefore, it is preferable that the release layer has a predetermined thickness. The thickness of the release layer 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, and the upper limit is 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.

[0124] In this specification, the thickness of the release layer is determined by measuring the thickness at 20 points on an image of the cross section of the transfer sheet taken using a scanning electron microscope (SEM), and averaging the values ​​at 20 points. The acceleration voltage of the SEM is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[0125] [Other layers] The releasable support constituting the transfer sheet of this embodiment may have layers other than the support and the release layer. Examples of layers other than the support and the release layer include an antistatic layer and an easy-adhesion layer.

[0126] <Transfer layer> The transfer layer is a layer that is transferred to an adherend. The transfer layer preferably has at least a release layer. Furthermore, the transfer layer more preferably has a release layer and an adhesive layer in this order from the releasable support side. Furthermore, 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 be positioned closer to the release layer than the decorative layer.

[0127] 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.

[0128] [Release layer] The release layer is a layer located on the outermost surface of the transfer layer when transferred to an adherend, and is a layer that can impart a surface shape to the adherend. For this reason, the release layer preferably has good surface properties such as scratch resistance, weather resistance, and contamination resistance.

[0129] The release layer preferably contains a resin as its main component, which means that the resin accounts for 50% by mass or more of the total solid content of the release layer, preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0130] The release layer preferably contains a cured product of a resin composition containing a curable resin as the resin, so that it can obtain surface properties such as scratch resistance, easily maintain the surface shape, and easily impart a desired surface shape. The proportion of the cured resin composition containing the curable resin relative to the total amount of resin contained in the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 100% by mass.

[0131] 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 it is easy to improve weather resistance since there is no restriction on the use of an ultraviolet absorber. A cured product of a resin composition containing an ionizing radiation curable resin is preferred because it can provide surface properties such as scratch resistance, easily maintains its surface shape, and can easily impart a desired surface shape. Among these, a cured product of a resin composition containing an electron beam curable resin is preferred because it can easily improve weather resistance while providing better scratch resistance and is not limited by the use of an ultraviolet absorber.

[0132] Examples of the resin composition containing a thermosetting resin for the release layer include those exemplified as the resin composition containing a thermosetting resin for the release layer. The composition contains at least a thermosetting resin, and is a resin composition that hardens when heated. Examples of the resin composition containing an ionizing radiation curable resin for the release layer include those exemplified as the resin composition containing an ionizing radiation curable resin for the matte layer.

[0133] The release layer may contain particles such as matting agents and wrinkle formation stabilizers, but preferably does not substantially contain such particles. By substantially not containing particles in the release layer, it is possible to prevent the release layer from having a decrease in scratch resistance, weather resistance, stain resistance, etc., which may be caused by the particles falling off. Furthermore, even if a matting agent is not contained, a sufficient matting effect can be obtained due to the surface shape, so a matting agent is not particularly necessary. 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.

[0134] In order to improve weather resistance, the release layer preferably contains an ultraviolet absorber or a light stabilizer, more preferably contains an ultraviolet absorber and a light stabilizer. The ultraviolet absorber and light stabilizer may be general-purpose compounds. Among ultraviolet absorbers, hydroxyphenyltriazine compounds are preferred. Among light stabilizers, hindered amine compounds are preferred.

[0135] The content of the ultraviolet absorber in the release layer is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 7 parts by mass, per 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 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 7 parts by mass, per 100 parts by mass of the resin in the release layer.

[0136] 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, in order to improve the handleability of the transfer sheet and the scratch resistance and weather resistance of the release layer.

[0137] [Adhesive layer] The adhesive layer is a layer formed as needed 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. Furthermore, if the transfer layer and the adherend can be closely attached 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, which will be described later.

[0138] 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 handleability of the transfer sheet and the adhesion between the transfer layer and the adherend. The heat-sensitive adhesive layer is sometimes called a heat-seal layer.

[0139] 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 selected appropriately from acrylic, urethane, silicone, rubber, and other adhesives.

[0140] 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 due to a chemical reaction caused by heat, and examples thereof 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).

[0141] When the adhesive layer is a heat-sensitive adhesive layer, the adhesive layer preferably contains a thermoplastic resin. Examples of thermoplastic resins include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, cyanoacrylate resins, and epoxy resins, which can be used alone or in combination. Among these, acrylic resins are preferred because of their good weather resistance.

[0142] The weight-average molecular weight of the thermoplastic resin is preferably 10,000 to 200,000, more preferably 50,000 to 150,000, and even 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 can be 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.

[0143] 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 this range, it is possible to easily improve the adhesion between the adhesive layer and the adherend, and it is also possible to easily improve the handleability of the transfer sheet.

[0144] 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 hiding properties of the transfer layer, thereby hiding the color and appearance of the surface of the adherend.

[0145] 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 flaky flakes of aluminum, brass, and the like; and pearlescent pigments such as flaky flakes of titanium dioxide-coated mica and basic lead carbonate, and the like.

[0146] 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, relative to 100 parts by mass of the resin constituting the adhesive layer. By setting the colorant content to 5 parts by mass or more, the design of the transfer layer can be easily improved, and by setting the colorant content to 90 parts by mass or less, a decrease in the adhesive strength of the adhesive layer can be easily suppressed.

[0147] [Primer layer] To improve the adhesion between the layers constituting the transfer layer, each layer of the transfer layer may be subjected to a surface treatment such as the physical surface treatment (oxidation method, roughening method, etc.) or chemical surface treatment, as necessary. A primer layer may be provided between each of these layers as an easy-adhesion layer, or these surface treatments may be used in combination with the primer layer. The primer layer may be formed, for example, 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 to position the primer layer 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.

[0148] 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.

[0149] Preferred examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins, and these can be used alone or in combination. 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 resin and crosslinking the resin to harden it. Among these, polycarbonate-based urethane-acrylic copolymers are preferred.

[0150] 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, and has good weather resistance. (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.

[0151] 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; and alicyclic isocyanates.

[0152] 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.

[0153] The mass ratio of the acrylic component to the urethane component in the polycarbonate-based urethane acrylic copolymer is preferably in the range of 95:5 to 30:70, more preferably 93:7 to 50:50, and even more preferably 90:10 to 60:40. By setting the mass ratio of the acrylic component to the urethane component in this range, the primer layer does not become an excessively hard coating film, sufficient processability is obtained, and when a primer layer is formed on the release layer, adhesion between the release layer and the primer layer is improved, which is preferable.

[0154] 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, and calcium carbonate, as well as organic particles. Among these, inorganic particles are preferred, and among inorganic particles, silica is preferred.

[0155] The average particle size of the anti-blocking agent is preferably about 0.1 to 10 μm, more preferably 0.5 to 8 μm, and even more preferably 0.5 to 5 μm. The particle size of the anti-blocking agent is measured as the mass average value d50 in particle size distribution measurement by laser 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, even more preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass, per 100 parts by mass of the binder resin.

[0156] The thickness of the primer layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

[0157] [Decorative layer] The transfer layer may have a decorative layer to enhance the design, and the decorative layer is preferably formed between the release layer and the adhesive layer.

[0158] The decorative layer may be formed on the entire surface of the transfer sheet, or may be formed on only a part of the surface.

[0159] Examples of the decorative layer include a colored layer formed by applying ink in a solid manner, a patterned 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 vessel 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; brickwork patterns including grooves; sand grain patterns; pear-skin patterns; patterns consisting of an arrangement of multiple concave and convex stripes extending 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 designs.

[0160] The ink used for the colored layer and the design layer is a mixture of a binder resin with an appropriate amount of a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, 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. Also, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

[0161] 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 to 90 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin constituting the decorative layer.

[0162] The color layer and the design layer may contain additives such as ultraviolet absorbers, light stabilizers, and colorants. The thickness of the colored layer and the patterned layer may be appropriately selected depending on the desired pattern, but to improve the design, it is preferably 0.5 μm to 20 μm, more preferably 1.0 μm to 10 μm, and even more preferably 1.5 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 this depends on the type and content of the colorant contained.

[0163] Examples of metal thin films include thin films of simple metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt, and thin films of alloys containing two or more of the above metal elements. Examples of alloys include brass, bronze, and stainless steel. The thickness of the metal thin film can be set to about 0.1 μm or more and 1 μm or less.

[0164] 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.

[0165] <separator> The transfer sheet may have a separator on the side of the transfer layer opposite to 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. For example, when the transfer sheet of this embodiment has the layer structure shown in Fig. 3, the separator is provided so as to contact the adhesive layer 24. When using the transfer sheet, the separator is peeled off, and the exposed adhesive layer is brought into contact with the adherend, and the sheet is used by laminating them together.

[0166] 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, known release agents such as fluorine-based release agents and silicone-based release agents can 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 10 μm or more and 200 μm or less, more preferably 15 μm or more and 150 μm or less, and even more preferably 20 μm or more and 100 μm or less.

[0167] [60° gloss value] The transfer sheet of this embodiment is capable of forming a transfer layer on an adherend that has an excellent matte effect and is easily visible. In this specification, "matte" means that the gloss is difficult to see, 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 20.0 or less, preferably 10.0 or less, is generally considered to be "matte." Furthermore, since the transfer sheet of this embodiment imparts a matte finish, the 60° gloss value refers to the 60° gloss value that can be imparted by the transfer sheet of this embodiment (the 60° gloss value of a decorative material obtained by transferring a transfer layer to an adherend).

[0168] If the transfer layer constituting the transfer sheet of this embodiment has a stable matte effect and texture due to stable wrinkle formation, the cosmetic material obtained by transferring the transfer layer to an adherend can also be a luxurious cosmetic material with a stable matte effect visibility and texture. The 60° gloss value of the releasable support that constitutes the transfer sheet and the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend will be basically the same if the two have similar color tones, although there will be some differences.

[0169] Up until now, for example, in the case of a decorative material that exhibits a dark color such as black, it has been possible to impart visibility with an excellent matte effect, such as a 60° gloss value of 20.0 or less, preferably 10.0 or less, by adding a matting agent to the matte layer. "Dark color" means a color with low brightness, for example, a color with a low brightness as measured in accordance with JIS Z8781-4:2013, such as CIE (Commission Internationale de l'Eclairage) L. * a * b * L in color space * value (hereinafter simply referred to as "L * This means that the 60° gloss value is usually about 40 or less, and preferably 30 or less. However, the use of a large amount of matting agent causes streaks and unevenness during the formation of the matte layer, making it difficult to manufacture and also reducing the strength of the matte layer. Furthermore, for decorative materials that exhibit colors other than dark colors, there is a limit to how much the 60° gloss value can be reduced even if a matting agent is added to the matte layer.

[0170] This tendency becomes more pronounced as the 60° gloss value becomes smaller. Therefore, in conventional techniques using matting agents, it is necessary to reduce the amount of matting agent used for manufacturing reasons, and it has not been possible to obtain a more excellent matting effect in terms of visibility.

[0171] In this embodiment, when forming the basic matte layer, two types of wrinkle formation stabilizers having a predetermined average particle size are used in combination, and the content is kept small as described above, thereby not only achieving a stable and extremely excellent matte effect in visibility and texture, but also achieving a rough tactile feel. Furthermore, by keeping the amount of wrinkle formation stabilizer used to an extremely small amount, a significant increase in viscosity of the resin composition is suppressed, thereby improving the productivity of the matte layer.

[0172] The 60° gloss value of a decorative material obtained using the transfer sheet of this embodiment cannot be generally defined because it varies depending on the color tone, as mentioned above, but when the decorative material exhibits black or other dark colors, for example, the 60° gloss value on the transfer layer side can be 10.0 or less, and further 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, or 2.0 or less, thereby achieving extremely excellent visibility of the matte effect. Furthermore, decorative materials exhibiting colors other than black and other dark colors can also have the above 60° gloss values.

[0173] In this specification, the 60° gloss value on the transfer layer side 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 locations from the transfer layer side 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.

[0174] [Transfer sheet manufacturing method] The transfer sheet of this embodiment can be produced, for example, as follows: The following production method is intended to produce a transfer sheet having the layer structure shown in FIG. The optical film can be produced through the steps of forming a releasable support, a release layer, a primer layer, a decorative layer, and an adhesive layer. The process for forming the release support is as described in the method for forming the surface shape of the transfer layer. A basic matte layer is prepared separately, a resin composition for forming the release layer is applied to the support, the surface shape of the basic matte layer is imprinted on the applied surface, and the resin composition is cured by irradiating with ultraviolet light or the like. It goes without saying that when the release support does not have a release layer and is only a support, the surface shape can be provided on the support. The conditions for curing the release layer can be appropriately selected depending on the type of resin composition of the release layer, and the resin composition can be cured by heating, irradiating with ultraviolet light, electron beams, or other ionizing radiation.

[0175] When electron beams are used as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the resin used and the layer thickness, but it is usually preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. The exposure dose is preferably an amount that saturates the crosslink density of the ionizing radiation-curable resin, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

[0176] The electron beam source is not particularly limited, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used. When ultraviolet light is used as the ionizing radiation, ultraviolet light having a wavelength of 190 to 380 nm is emitted. There are no particular limitations on the ultraviolet light source, and examples that can be used include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

[0177] Next, a resin composition for forming a release layer is applied onto the cured release layer and cured in the same manner as in the release layer.

[0178] The 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 each layer 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 liquid as necessary.

[0179] [Manufacturing method for decorative materials] The method for producing a decorative material of this embodiment includes the following steps (I) and (II). (I) A step of obtaining a laminate in which the transfer layer side of the transfer sheet of the present embodiment is adhered to an adherend. (II) A step of peeling off the releasable support from the laminate to obtain a decorative material having a transfer layer on an adherend.

[0180] The adherend in step (I) is not particularly limited, and adherends made of resin, paper, nonwoven fabric, woven fabric, wood, metal, nonmetallic inorganic material, etc. can be appropriately selected. When a resin is used as the adherend, physical or chemical surface treatments such as oxidation and roughening can be applied to one or both sides as desired to improve adhesion between the transfer layer of the transfer sheet and the adherend. The shape of the adherend is not particularly limited, and may be a flat plate such as a sheet, or may have a three-dimensional shape such as a curved plate or polygonal pillar.

[0181] In step (I), 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 (I).

[0182] One embodiment of step (I) is a lamination method having the following steps (a1) and (a2) in order: (a1) A step of contacting and superimposing the transfer layer side of the transfer sheet on the adherend on a flat plate. (a2) A step of applying heat and / or pressure from the releasable support 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.

[0183] Another embodiment of step (I) is an in-mold molding method that requires the following steps (z1) to (z4) in order: In 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 forming 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, thereby forming a resin molded body. (z4) A step of removing the resin molded body from the in-mold molding die.

[0184] 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 step (1). (0) A step of peeling the separator from the transfer sheet.

[0185] The decorative material obtained as described above can be cut as desired and the surface or end grain can be decorated with grooves, chamfers, etc. using a cutting machine such as a router or cutter. It can be used for a variety of 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; fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other fixtures; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative panels for cabinets and other appliances and office automation equipment; interior and exterior components for vehicles; signboards; soundproof walls; and even packaging materials and antiglare films for displays. That is, the transfer sheet of this embodiment is suitable for use as a transfer sheet for transferring uneven patterns to these various components. Among the decorative materials, resin decorative panels are preferably used mainly as surface decorative panels for general furniture such as chests of drawers, shelves, and desks, as well as for fixtures such as doors, and as various counters.

[0186] [Decorative materials] The decorative material of this embodiment is a decorative material having a transfer layer on an adherend, and at least a part of the surface of the transfer layer opposite to the adherend, ISO25178 The Spc (arithmetic mean curvature of the apex of the protrusion) specified in -1 The surface shape is larger than the above, and has a Rsm (average length of curved elements) specified in JIS B0601:2013 of 30 μm or more.

[0187] Fig. 6 is a cross-sectional view showing one embodiment of a decorative material 200 of the present invention. The decorative material 200 in Fig. 6 has a transfer layer 20 on an adherend 30. In Fig. 6, the transfer layer 20 has, in this order from the side closest to the adherend 30, an adhesive layer 24, a decorative layer 23, a primer layer 22, and a release layer 21. In the decorative material of Fig. 6, a release layer 21 is located on the surface of the transfer layer 20 opposite to the adherend 30. Therefore, in the decorative material of Fig. 6, at least a part of the surface of the release layer 21 opposite to the adherend 30 has a curvature of 4000 mm (arithmetic mean curvature of the apex of the protrusions) Spc. -1 The surface shape is larger than the surface roughness, and has a Rsm (average length of curved elements) of 30 μm or more.

[0188] Examples of the adherend that constitutes the decorative material of this embodiment include the adherends exemplified in the manufacturing method for the decorative material of this embodiment. Examples of the transfer layer that constitutes the decorative material of this embodiment include the transfer layer exemplified in the transfer sheet of this embodiment. [Example]

[0189] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0190] 1. Evaluation 1-1. Surface shape measurement The surface shape of the peelable layer side of the decorative materials obtained in the examples and comparative examples was measured for Spc (arithmetic mean curvature of the apex of the protrusions), Rsm (average length of the curved elements), Rz (maximum height), and Ra (arithmetic mean roughness). The measurement area was a rectangle (1024 μm × 768 μm) at an arbitrary location on the surface of the decorative material, and was measured using a shape analysis laser microscope ("VK-X150 (controller) / VK-X160 (measurement unit)", manufactured by Keyence Corporation) with an objective lens of 50x, a laser wavelength of 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, and measurement quality: high-speed mode.

[0191] The cutoff values ​​for Rsm (average length of curved elements), Rz (maximum height), and Ra (arithmetic mean roughness) were set to 0.8 mm. The surface shape of the release layer side of the decorative material can be considered to be the surface shape of the transfer layer on the releasable support side.

[0192] 1-2.60° gloss value A black plate was attached to the back of the polycarbonate resin plate of the decorative material obtained in the examples and comparative examples via an adhesive layer to prepare samples. 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) in accordance with K 5600-4-7:1999.

[0193] 1-3. Evaluation of texture before weather resistance test The cosmetic materials obtained in the Examples and Comparative Examples were evaluated by 20 random adults for surface texture (uniformity of surface condition) and rated according to the following criteria. A: 18 or more people evaluated that the surface condition was uniform and the matte effect was 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 people evaluated that the surface condition was uniform and the matte effect was highly visible.

[0194] 1-4. 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 decorative materials were evaluated for surface texture (uniformity of surface condition) using the same criteria as in 1-3.

[0195] <Weather resistance test> A weather resistance test was carried out using a weather resistance tester (trade name "Metal Weather" manufactured by Daipla Wintes Co., Ltd.) In the weather resistance test, the following "ultraviolet light irradiation process," "condensation process," and "water spray process" were defined as one cycle, and this cycle was repeated for 500 hours.

[0196] 《Ultraviolet irradiation process》 Illuminance: 60mW / cm 2 Black panel temperature: 63°C, chamber humidity: 50%RH, time: 20 hours 《Condensation process》 Illuminance: 0mW / cm 2 Black panel temperature: 30℃, chamber humidity: 98%RH, time: 4 hours 《Water spray process》 Spray water for 10 seconds before and after the condensation process.

[0197] (Evaluation of rough texture) For the cosmetic materials obtained in the Examples and Comparative Examples, 20 random adults were asked to evaluate the surface texture of an Oxford cloth made of 40-count cotton yarn as a standard for roughness, and the evaluation was based on the following criteria. A: More than 18 people rated the texture as close to the standard and as rough. B: Between 15 and 17 people rated the texture as close to the standard and as rough. C: 14 or less people evaluated that the texture was close to the standard and that it was rough to the touch.

[0198] 2. Preparation of matte layer and mold creation from matte layer [Basic matte layer] A colored thin paper base paper for building materials (thickness: 30 μm) was used as the substrate, and a resin composition containing acrylic resin and urethane resin as binder resins was applied to one side of the substrate and dried to form an easy-adhesion layer (thickness: 2 μm). Resin composition 1 for forming the basic matte layer described later was applied onto the easy-adhesion layer by gravure coating (amount applied: 5 μm (when dried)), and then irradiated with ultraviolet light using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet light amount: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet 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 (ultraviolet light output density: 200 W / cm) to obtain a laminate (1) having a matte layer on the substrate.

[0199] A resin composition containing acrylic resin and urethane resin as binder resins was applied to one side of a support (a corona discharge-treated PET sheet, thickness: 100 μm) and dried to form an easy-adhesion layer (thickness: 2 μm). Next, the curable resin of the following laminate (2) (for forming a release layer) was applied onto the easy-adhesion layer by gravure coating to form a coating film (coating amount: 5 μm (when dried)), thereby obtaining a laminate (2) having an easy-adhesion layer and an uncured release layer on the support.

[0200] Next, the surface of the obtained laminate (1) on the side of the basic matte layer was dry laminated onto the uncured coating film (uncured release layer) of the laminate (2), to obtain a laminate (2'). Next, the PET side of the laminate (2) constituting the laminate (2') was irradiated with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to cure the uncured curable resin. Next, the laminate (1) was peeled off from the laminate (2') to obtain a release support having an easy-adhesion layer and a release layer on the support, which was used in Example 1. The surface of the release support was formed with a shape that was the inverse of the surface shape of the basic matte layer.

[0201] <Resin composition 1 for forming basic matte layer> 60 parts by weight of multifunctional urethane acrylate oligomer (functional group number: 4) 30 parts by weight of polyfunctional acrylate monomer (bifunctional) 10 parts by mass of monofunctional acrylate monomer Wrinkle formation stabilizer (silica particles, average particle size: 5 nm) 3 parts by weight 0.8 parts by mass of photopolymerization initiator (benzophenone type)

[0202] <Curable resin for laminate (2) (for forming release layer)> Urethane acrylate oligomer 100 parts Reactive acrylic-modified silicone oil 0.5 parts (used as a release agent)

[0203] 3. Preparation of transfer sheets and decorative materials [Example 1] On the release layer of the releasable support obtained above, the resin composition 1 for forming the release layer described below was applied to form an uncured resin layer, and the uncured resin layer was cured by irradiating 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.

[0204] Next, a resin composition for forming a primer layer, which will be described later, 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 heat-sealable adhesive layer. After forming the adhesive layer, the sheet was aged at room temperature for 24 hours to obtain the transfer sheet of Example 1.

[0205] 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 "Carbopolish"), and laminated. Then, using a laminator (a roll-type thermal transfer machine manufactured by Navitas Co., Ltd., product name "RT-300"), pressure was applied from the transfer sheet side while heating under conditions of a lamination roll temperature of 160°C and a conveyance 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. Next, the releasable support 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.

[0206] <Resin composition 1 for forming release layer> Ionizing radiation curable resin (bifunctional urethane oligomer): 100 parts by mass Ultraviolet absorber (BASF, product name: Tinuvin 479): 0.5 parts by mass Light stabilizer (BASF, trade name: Tinuvin 123): 0.3 parts by mass

[0207] <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 mass Ultraviolet absorber (BASF, product name: Tinuvin 400): 15 parts by mass Light stabilizer (BASF, trade 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

[0208] [Example 2] A decorative material of Example 2 was obtained in the same manner as in Example 1, except that Resin composition 1 for forming a release layer was changed to Resin composition 2 for forming a release layer. <Resin composition 2 for forming release layer> Bifunctional urethane acrylate oligomer: 40 parts by mass Hexafunctional urethane acrylate oligomer: 60 parts by weight Ultraviolet absorber (BASF, product name: Tinuvin 479): 2 parts by mass Light stabilizer (Nippon Nyukazai Co., Ltd., product name: Sanol LS-3410): 3 parts by mass

[0209] [Comparative Example 1] In the [Matte layer 1] of "2" above, the substrate was changed to a PET sheet (Cosmoshine (registered trademark) A4160 (50 μm) manufactured by Toyobo Co., Ltd.), and the resin composition 1 for forming the matte layer was applied to the adhesive surface of the substrate by the gravure method (application amount: 18 μm (when dry)). The release support, transfer sheet and decorative material of Comparative Example 1 were obtained in the same manner as in Example 1.

[0210] Comparative Example 2 A releasable support, transfer sheet and decorative material of Comparative Example 2 were obtained in the same manner as in Comparative Example 1, except that the amount of resin composition 1 for forming the matte layer was changed to 5 μm (when dried).

[0211] Comparative Example 3 In Example 1, the substrate of [Matte layer 1] of "2" was changed to a polypropylene sheet (PP, thickness: 100 μm) that had been subjected to corona discharge treatment, a resin composition for forming a primer layer (urethane resin, coating amount: 2 μm (when dry)) was applied to one side of the substrate, and the resin composition 1 for forming the matte layer was applied on the primer layer (coating amount: 5 μm (when dry)).The same procedure was repeated to obtain a release support, transfer sheet, and decorative material of Comparative Example 3.

[0212] Comparative Example 4 In Comparative Example 2, the release support, transfer sheet and decorative material of Comparative Example 4 were obtained in the same manner, except that ultraviolet light was not irradiated using a UV irradiation device consisting of the LED of [Matte layer 1] of ``2'' above.

[0213] Comparative Example 5 In Comparative Example 1, the release support, transfer sheet and decorative material of Comparative Example 5 were obtained in the same manner, except that Resin composition 1 for forming the matte layer was changed to Resin composition 2 for forming the basic matte layer described below. <Resin composition 2 for forming basic matte layer> 60 parts by weight of multifunctional urethane acrylate oligomer (functional groups: 7) 30 parts by weight of polyfunctional acrylate monomer (bifunctional) 10 parts by mass of monofunctional acrylate monomer Wrinkle formation stabilizer (silica particles, average particle size: 5 nm) 15 parts by weight 0.8 parts by mass of photopolymerization initiator (benzophenone type)

[0214] Comparative Example 6 A releasable support, transfer sheet and decorative material of Comparative Example 6 were obtained in the same manner as in Comparative Example 5, except that the coating amount of the resin composition 2 for forming the matte layer was changed to 5 μm (when dried).

[0215] The releasable supports, transfer sheets, and decorative materials obtained in Examples 1 and 2 and Comparative Examples 1 to 6 were evaluated for Spc (arithmetic mean curvature of the apexes of the protrusions), Rsm (average length of the curved elements), Rz, Ra, and 60° gloss, as well as for texture (before weather resistance test), texture (after weather resistance test), and roughness to the touch. These results are shown in Table 1. 7 to 13 show micrographs of the surfaces of the decorative materials obtained in Example 1 and Comparative Examples 1 to 6.

[0216] [Table 1]

[0217] The results in Table 1 confirm that the matte article of this embodiment has a 60° gloss value of 1.3 to 1.4 on the matte layer side, and is an article with extremely excellent visibility of the matte effect and excellent texture. It was also confirmed that the article has an excellent rough texture.

[0218] On the other hand, it was found that the matte articles of Comparative Examples 1 to 3, in which the Rsm was less than 30 μm, had poor texture and did not have a rough feel to the touch. -1 The matte articles of Comparative Examples 4 to 6 below had 60° gloss values ​​of 3.5 to 5.6, and were found to have textures that were even inferior to the matte articles of Comparative Examples 1 to 3. The matte articles of Comparative Examples 4 to 6 were also found to have a rough texture that was inferior to Example 1. [Industrial Applicability]

[0219] The transfer sheet of the present embodiment can impart excellent matte visibility and texture, and can also impart a rough feel to the touch, and is therefore suitable for a variety of applications, including interior building components such as walls, ceilings, and floors; exterior building components such as exterior walls, eaves ceilings, roofs, fences, and fences; fixtures and fittings such as window frames, doors, door frames, handrails, baseboards, moldings, and other fixtures; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative panels for cabinets for home appliances and office automation equipment; and interior and exterior components for vehicles. In addition to the decorative materials used in the aforementioned buildings and the like, the transfer sheet of this embodiment can be laminated, composited, or combined with other materials (adherends) and suitably used as packaging materials, anti-glare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various certificates, various keyboard keys, transparent panels (window glass, etc.) for windows, doors, partitions, etc., signs, soundproof walls, artificial leather, etc. [Explanation of symbols]

[0220] 1a: Protrusion apex (Spc large) 1b: Protrusion apex (Spc small) 2: Convex part 2a: Convex part (Rsm small) 2b: Convex part (large Rsm) 2c, 2d: Convex part 3: Recess 3a~3c: Concave part 10: Releasable support 11:Support 12: Release layer 20: Transfer layer 21: Peel layer 22: Primer layer 23: Decorative layer 24: Adhesive layer 30: Adherent material 100: Transfer sheet 200: Cosmetic materials

Claims

1. A transfer sheet having a transfer layer on a releasable support, At least a part of the surface of the transfer layer on the side of the releasable support has an Spc (arithmetic mean curvature of the apex of the protrusion) defined in ISO 25178 of 4000 mm －１ A transfer sheet having a surface shape in which the Rsm (average length of curved elements) at a cutoff value of 0.8 mm as specified in JIS B0601:2013 is 30 μm or more.

2. The transfer sheet according to claim 1, wherein Rz (maximum height), which is a parameter of peaks and height of a profile curve of the surface shape defined in JIS B0601:2013, is 8.00 μm or more and 30.00 μm or less.

3. The transfer sheet according to claim 1 or 2, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of a profile curve of the surface shape defined in JIS B0601:2013, is 1.00 μm or more and 5.50 μm or less.

4. 4. The transfer sheet according to claim 1, wherein the surface of the transfer layer that forms the surface shape has an uneven shape formed by irregular wrinkles.

5. The transfer sheet according to claim 4 , wherein the irregular wrinkles are composed of 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.

6. 6. The transfer sheet according to claim 1, wherein the transfer layer comprises a release layer and an adhesive layer in this order from the releasable support side.

7. The transfer sheet according to claim 6, further comprising at least one layer selected from a primer layer and a decorative layer between the release layer and the adhesive layer.

8. The transfer sheet according to claim 6 or 7, wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation curable resin.

9. 9. The transfer sheet according to claim 6, wherein the release layer contains an ultraviolet absorber or a light stabilizer.

10. The transfer sheet according to any one of claims 6 to 9, wherein the release layer is substantially free of particles.

11. The transfer sheet according to any one of claims 1 to 10, wherein the releasable support has a release layer on the support.

12. The transfer sheet according to claim 11, wherein the release layer comprises a cured product of a resin composition containing an ionizing radiation curable resin.

13. A method for producing a decorative material, comprising the following steps (1) and (2): (1) A step of obtaining a laminate in which the transfer layer of the transfer sheet according to any one of claims 1 to 12 is closely attached 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 the adherend.

14. A decorative material having a transfer layer on an adherend, At least a part of the surface of the transfer layer opposite to the adherend has an Spc (arithmetic mean curvature of the apex of the protrusion) defined in ISO 25178 of 4000 mm －１ A decorative material having a surface shape in which the Rsm (average length of curved elements) at a cutoff value of 0.8 mm as specified in JIS B0601:2013 is 30 μm or more.

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