Transfer sheet, method for manufacturing a cosmetic material using the same, and cosmetic material

Abstract

To provide a transfer sheet which has excellent visibility and texture of matting effects, and excellent rough touch feeling.SOLUTION: A transfer sheet has a transfer layer on a releasable support, and has a surface shape of Ssk (skewness) of 0.00 or more and Sku (kurtosis) of more than 3.50, which are defined in ISO 25178-2:2012, on at least a part of the surface on the releasable support side of the transfer layer.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Conventionally, for example, interior members of buildings such as walls, ceilings, and floors, exterior members such as exterior walls, eaves, roofs, fences, and fences, window frames, doors, door frames, handrails, baseboards, moldings, and moldings, as well as general furniture such as wardrobes, shelves, and desks, kitchen furniture such as dining tables and sinks, various furniture and members used in wet areas such as kitchens, toilets, bathrooms, and washbasins, or surface decorative boards for cabinets of home appliances, OA equipment, etc., and interior or exterior members of vehicles, etc. So-called decorative materials and decorative sheets are used as articles for decorating and protecting the surfaces. As such decorative materials and decorative sheets, for example, those having a surface layer with desired functions are used, and various performances such as surface characteristics mainly including scratch resistance, stain resistance, and weather resistance, and processing characteristics are required.

[0003] For the decorative materials used in these applications, a technique of improving the texture by using a dulling effect (mat effect) to improve the design property is widely used. As a decorative material using a dulling effect, for example, Patent Document 1 proposes a decorative sheet having a pattern layer and a concealing layer on one side of a base sheet and a gloss adjustment layer (mat layer, gloss layer) on the other side. In the decorative sheet of Patent Document 1, due to the difference in gloss between the mat layer and the gloss layer of the gloss adjustment layer, a design effect of highlighting the pattern layer and the concealing layer is obtained. In its example, a mat ink obtained by adding a total of 50 parts by weight of a dulling agent, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of the resin component, is used for the mat layer provided on the entire surface.

[0004] Further, Patent Document 2 proposes a decorative material having a printing layer and a transparent resin layer in this order on a base material, and an embossed pattern is provided 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] [Problems to be Solved by the Invention]

[0006] As a method for improving the texture by a matting effect (matte effect), there are mainly methods such as using a matting agent (also referred to as a “matting agent”) as in Patent Document 1 above and obtaining a matting effect by the light diffusion effect it has, and a method of forming an uneven shape (also referred to as an uneven pattern) on the outermost surface by performing embossing as in Patent Document 2 above. However, when using a matting agent as in Patent Document 1, in order to make the matting effect better, it is necessary to increase its usage amount. However, as the usage amount increases, the matting agent falls off from the coating film, and the coating film is damaged, resulting in a decrease in scratch resistance. Also, due to the change in gloss caused by the lack of the matting agent, scratches are more likely to be noticeable. Or, contaminants penetrate into the minute gaps at the interface between the matting agent and the resin, and furthermore, contaminants are adsorbed onto the matting agent itself, resulting in a decrease in stain resistance. For these reasons, the surface characteristics tend to deteriorate. On the other hand, if the usage amount is reduced to suppress the deterioration of the surface characteristics, the matting effect tends to decrease, and there is a trade-off relationship between the surface characteristics and the matting effect. Therefore, there is a limit to the matting effect using a matting agent. Also, when using embossing as in Patent Document 2, the production of the embossing plate is time-consuming and not easy, and furthermore, it is necessary to produce a plate for each desired pattern. Therefore, it cannot be said that it is a method that can easily meet the diversity of customer needs. Also, in the embossing of Patent Document 2, the manufacturing process may be restricted, or it may be difficult to impart an uneven shape depending on the material of the article to which the uneven shape is to be imparted.

[0007] By the way, the diversity of customer needs is wide-ranging, and not only the above-mentioned visual dulling effect but also tactile expressions are increasingly demanded. For example, when using a dulling agent as in the above Patent Document 1, by increasing its usage amount, the contour of the dulling agent appears on the surface of the decorative sheet, and a somewhat rough tactile sensation may be felt. Also, when using embossing as in Patent Document 2, a tactile sensation may occur due to the uneven shape of the surface formed by the embossing plate. However, in either case, the focus is not on the expression of the tactile sensation, and the situation is such that it cannot be said that sufficient expression is achieved in terms of the tactile sensation. That is, conventional decorative sheets could not achieve both an excellent dulling effect and a tactile sensation. In the present invention, particular attention is paid to a "rough" tactile sensation among tactile sensations. Furthermore, as an embodiment of imparting design properties to the surface of an article such as a decorative sheet, it is often the case that both an uneven shape and a decorative layer such as a pattern layer are imparted. In that case, in the inventions disclosed in Patent Document 1 and Patent Document 2, since two different processes, namely a printing process for forming a pattern layer on a base material and an embossing process for shaping an uneven shape, are required, there is also a problem that the process time becomes long and the manufacturing cost also increases.

[0008] An object of the present invention is to provide a transfer sheet having excellent visibility and texture of a dulling effect and excellent in a rough tactile sensation, as well as a method for manufacturing a decorative material and a decorative material using the same.

Means for Solving the Problems

[0009] In order to solve the above problems, the present invention provides the following [1] to [3]. [1] A transfer sheet having a transfer layer on a release support, wherein at least a part of the surface of the transfer layer on the release support side has a surface shape defined in ISO25178-2:2012, where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50. [2] A method for manufacturing a decorative material having the following steps (1) and (2). (1) A step of obtaining a laminate in which the transfer layer of the transfer sheet described in [1] is in close contact with an adherend. (2) A step of peeling the release support from the laminate to obtain a decorative material having a transfer layer on the adherend. [3] A decorative material having a transfer layer on an adherend, wherein at least a part of the surface of the transfer layer on the side opposite to the adherend has a surface shape defined in ISO 25178-2:2012, where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50, the decorative material. [3] [Advantages of the Invention]

[0010] According to the present invention, it is possible to provide a transfer sheet having excellent visibility and texture of a matting effect and excellent in a rough touch. Further, according to the present invention, it is possible to easily manufacture a decorative material having excellent visibility and texture of a matting effect and excellent in a rough touch. [Brief Description of the Drawings]

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Embodiments for Carrying Out the Invention

[0012] [Transfer Sheet] Hereinafter, embodiments of the present invention (hereinafter sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values related to "above", "below" and "~" regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values of the examples are numerical values that can be used as the upper and lower limits of the numerical range.

[0013] 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 side of the releasable support has a surface shape defined in ISO25178-2:2012, where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50.

[0014] FIG. 3 is a cross-sectional view showing an embodiment of the transfer sheet 100 of the present invention. The transfer sheet 100 in FIG. 3 has a transfer layer 20 on a releasable support 10. Further, in FIG. 3, the releasable support 10 has a release layer 12 on a support 11. Further, in FIG. 3, the transfer layer 20 has a release layer 21, a primer layer 22, a decorative layer 23, and an adhesive layer 24 in this order from the side closer to the releasable support 10. In the transfer sheet of FIG. 3, a release layer 21 is located on the side of the transfer layer 20 closer to the releasable support 10. Therefore, in the transfer sheet of FIG. 3, at least a part of the surface of the release layer 21, which is the surface of the transfer layer 20 on the side of the releasable support 10, has a surface shape where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50.

[0015] 〔Regarding the surface shape〕 The surface shape that the transfer sheet of the present embodiment has on at least a part of the surface of the transfer layer on the side of the releasable support (hereinafter also simply referred to as "the surface shape of the transfer layer" or "the surface shape") will be described. The surface shape of the transfer layer is reflected as the surface shape of the decorative material formed by transferring the transfer layer onto the adherend. As described above, although the surface shape of the transfer layer is reflected as the surface shape of the decorative material formed by transferring the transfer layer onto the adherend, the surface shape of the transfer layer and the surface shape of the decorative material are not limited to being exactly the same and may vary slightly depending on the conditions of heat and pressure during transfer. The surface shape is required to have Ssk (skewness) of 0.00 or more and Sku (kurtosis) of more than 3.50 as defined in ISO25178-2:2012. By having such a surface shape, the transfer sheet of the present embodiment can impart excellent visibility and texture of the matte effect (hereinafter, these may be collectively referred to as the "matte effect") to the adherend, and can also impart a particularly "coarse" tactile sensation to the adherend as a tactile sensation. The "coarse" tactile sensation is a sensory expression, but the "coarse" in this specification generally includes all tactile sensations that are generally felt as "coarse". Specifically, it means the tactile sensation felt when touching a rough surface with the pad of a finger, and can also be said to be a tactile sensation that is rough and not smooth, with a prickly feeling of roughness. Examples of those having a "coarse" tactile sensation include, for example, a coarse cotton fabric such as an Oxford fabric using a relatively thick thread of about 10 to 50 counts (thick to medium count), or a hemp fabric using a relatively thick thread of about 10 to 50 counts.

[0016] Ssk (Skewness) is one of the three-dimensional surface texture parameters defined by the above ISO and is an index indicating the degree of deviation of the height distribution from the average plane. When Ssk is 0, the surface shape is symmetric (normal distribution) with respect to the average plane. When Ssk exceeds 0, it can be understood that the surface shape is biased downward with respect to the average plane, that is, the lower side in terms of height, and the vicinity of the top of the convex part tends to be sharp and thin. On the other hand, when Ssk is less than 0, it can be understood that the surface shape is biased upward with respect to the average plane (average level plane (horizontal line in FIGS. 1 and 2)), that is, the higher side in terms of height, and the vicinity of the top of the convex part tends to be blunt and thick. The tendency of the shape exhibited by the surface shape indicated by Ssk (Skewness) will be described with reference to FIG. 1. FIG. 1 is a schematic diagram of the case where Ssk (Skewness) exceeds 0 (1-1) and the case where it is less than 0 (1-2). That the Ssk (Skewness) of the surface shape in the present embodiment is 0.00 or more indicates that it tends to have the shape shown in (1-1). That is, since the surface shape is biased downward with respect to the average plane (average level plane (horizontal line in FIG. 1)), as the surface shape above the average plane, that is, the surface shape imparted by the transfer sheet of the present embodiment, there are more convex parts with a narrow width with respect to the height (high aspect ratio) and an elongated cross-sectional shape, and it can be said that they are distributed while having a certain distance. In relation to Sku (Kurtosis) described later, from the viewpoint of improving the matting effect and the rough touch, Ssk (Skewness) is preferably 0.30 or more, more preferably 0.50 or more, still more preferably 0.75 or more, and even more preferably 1.00 or more. There is no particular limitation on the upper limit, but from the viewpoint of ease of manufacturing, etc., it is usually about 3.50 or less, preferably 3.00 or less, and more preferably 2.75 or less.

[0017] The measurement of Ssk (skewness) is a measured value obtained by using a shape analysis laser microscope for a rectangle (1024 μm × 768 μm) at any location on the surface shape of the transfer layer. The surface shape of the transfer layer can be measured after transferring the transfer layer onto the adherend. The measurement conditions can be adjusted as appropriate. For example, it can be measured under the conditions described in the examples. Also, Sku (kurtosis), Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) regarding the contour curve, which will be described later, can be measured in the same manner.

[0018] Sku (kurtosis) is one of the three-dimensional surface property parameters defined by the above ISO and is an index indicating the degree of sharpness of the height distribution from the mean plane. When Sku is 3, the surface shape is symmetric (normal distribution) with respect to the mean plane. When Sku exceeds 3, the height distribution has a sharp shape, and when Sku is less than 3, it can be understood that the height distribution tends to be flattened. The tendency of the shape presented by the surface shape indicated by Sku (kurtosis) will be described with reference to FIG. 2. FIG. 2 is a schematic diagram when Sku (kurtosis) exceeds 3.000 (2-1) and when it is less than 3.00 (2-2). The fact that Sku (kurtosis) of the surface shape in the present embodiment exceeds 3.50 indicates that it tends to have the shape shown in (2-1) more prominently. That is, the surface shape has a height distribution with a sharp shape, with the most height portions around the average height, and few portions where the height is significantly higher or lower than the average height. It can be said that the tip shape of the convex portion existing above the mean plane has a sharp shape but the number is small. In relation to the aforementioned Ssk (skewness), from the viewpoint of improving the matting effect and the rough touch, Sku (kurtosis) is preferably 3.60 or more, more preferably 3.70 or more, and still more preferably 3.80 or more. There is no particular limitation on the upper limit, but from the viewpoint of ease of manufacturing, etc., it is about 10.00 or less, preferably 9.00 or less, and more preferably 8.00 or less.

[0019] As described above, the surface shape of the transfer layer of this embodiment has specific Ssk (skewness) and Sku (kurtosis). Due to the definition of Ssk (skewness), there are more convex portions with a narrow width relative to the height (higher aspect ratio) and an elongated cross-sectional shape, which are distributed while maintaining a certain distance. And it also has the feature that on the region of the convex portions due to the definition of Sku (kurtosis), protruding portions with a pointed tip shape and concave portions (acute-angled) with a sunken bottom are scattered. Since its tip shape is pointed and many elongated convex portions are scattered, when touching with the fingertip, a pointed tip shape can be felt with an appropriate contact frequency, which is considered to lead to the tactile sensation felt when touching a rough surface with the fingertip, a tactile sensation that is not smooth and rough, with a prickly roughness, that is, a "coarse" tactile sensation. Also, due to the existence of such convex portions, it is considered that a dulling effect is obtained because there are relatively concave portions. Details of the manifestation of the dulling effect will be described later.

[0020] The surface shape of the transfer layer of this embodiment preferably has minute wrinkles that are visually recognized in a plan view shown in FIG. 5 described later. Regarding the surface shape of the transfer layer of this embodiment, Ssk (skewness) and Sku (kurtosis), as well as Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) described later, are likely to be within a specific numerical range by having such minute wrinkles. Also, such minute wrinkles are likely to be formed by having Ssk (skewness) and Sku (kurtosis) within a specific numerical range, as well as Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) within a specific numerical range. Thus, it can be said that Ssk (skewness) and Sku (kurtosis), etc. and minute wrinkles are in an inseparable relationship. And by having such a surface shape, the dulling effect is improved together with a coarse tactile sensation.

[0021] In the present embodiment, as the surface shape, it is preferable that Rsm (average length of curve elements), which is a lateral parameter of the contour curve defined in JIS B0601:2013, is 100.00 μm or less. Rsm (average length of curve elements) is a lateral parameter of the contour curve and is the average of the lengths of the contour curve elements at the reference length. The larger the value of Rsm (average length of curve elements), the wider the width of the convex portion becomes, indicating an index that the surface shape tends to have wider convex portions. Therefore, in a surface shape that satisfies the above Ssk (skewness) and Sku (kurtosis), when Rsm (average length of curve elements) is 100.00 μm or less, the width of the convex portion of the surface shape becomes narrower, and the characteristic that the tip shape of the convex portion is sharp according to the above-mentioned definition of Sku (kurtosis) is emphasized, improving the rough touch. Also, the matting effect is improved. From the viewpoint of improving the matting effect and the rough touch, Rsm (average length of curve elements) is preferably 90.00 μm or less, more preferably 75.00 μm or less, still more preferably 60.00 μm or less, and even more preferably 50.00 μm or less. As the lower limit, it is 30.00 μm or more, more preferably 33.00 μm or more, still more preferably 35.00 μm or more. In the measurement of Rsm (average length of curve elements) in this specification, the cut-off value is 0.8 mm.

[0022] In the present embodiment, as the surface shape, it is preferable that Rz (maximum height), which is a lateral parameter of the contour curve defined in JIS B0601:2013, is 8.00 μm or more. Rz (maximum height) is one of the peak and height parameters of the contour curve, and is the sum of the height of the highest peak and the depth of the deepest valley in the contour curve at the reference length. The larger the value of Rz (maximum height), the larger (higher) the convex portions are in terms of shape as viewed from the valleys, and it serves as an indicator showing that there tends to be a large number of such convex portions. Therefore, in the surface shape satisfying the above Ssk (skewness) and Sku (kurtosis), when Rz (maximum height) is 8.00 μm or more, the characteristic that the tip shape of the convex portion is sharp according to the above-mentioned regulation of Sku (kurtosis) is emphasized, and the rough touch is improved. Also, the matting effect is improved. From the viewpoint of improving the matting effect and the rough touch, Rz (maximum height) is preferably 8.50 μm or more, more preferably 9.00 μm or more, still more preferably 9.50 μm or more, and the upper limit is preferably 30.00 μm or less, more preferably 26.00 μm or less, still more preferably 22.00 μm or less. In addition, when measuring Rz (maximum height) in this specification, the cut-off value is 0.8 mm.

[0023] In the present embodiment, as the surface shape, it is preferable that Ra (arithmetic mean roughness), which is a lateral parameter of the contour curve defined in JIS B0601:2013, is 5.50 μm or less. Ra (arithmetic mean roughness) is one of the height-direction parameters of the contour curve, and is the average value of the height differences from the average plane in the contour curve at the reference length. The smaller the value of Ra (arithmetic mean roughness), the smaller the convex portions in the surface shape and the corresponding concave portions formed thereby tend to be, and it is an indicator showing that the surface shape tends to be smoother and more uniform. Therefore, in the surface shape satisfying the above Ssk (skewness) and Sku (kurtosis), when Ra (arithmetic mean roughness) is 5.50 μm or less, the shapes of the convex portions of the surface shape are more likely to be more uniform and gentle, so that the abrupt touch is suppressed, and in particular, the rough touch is improved. Also, the matting effect is improved. From the viewpoints of improving the matting effect and the rough touch, Ra (arithmetic mean roughness) is preferably 5.25 μm or less, more preferably 5.00 μm or less, still more preferably 4.50 μm or less, and preferably 1.00 μm or more, more preferably 1.50 μm or more, still more preferably 1.75 μm or more as the lower limit. In addition, when measuring Ra (arithmetic mean roughness) in this specification, the cut-off value is 0.8 mm.

[0024] The surface shape of the transfer layer of this embodiment preferably has wrinkles. By stabilizing the formation of wrinkles on the surface of the transfer layer, a matting effect is stably exhibited due to the light diffusion effect caused by the shape of the wrinkles, and a layer that also exhibits a rough touch is formed. FIG. 5 is a schematic diagram in a plan view showing an embodiment of the transfer layer of the transfer sheet of this embodiment, and is a schematic representation of an image of the surface on the transfer layer side of the decorative material obtained in the example. FIG. 5 shows that wrinkles are formed on the surface of the transfer layer of this embodiment. Here, "plan view" means looking at the surface of the transfer layer from the positive Z-axis direction in the XYZ coordinate system shown in FIGS. 3 to 5.

[0025] The wrinkles formed on at least one surface of the transfer layer are not particularly limited as long as they have a surface shape having Ssk (skewness) and Sku (kurtosis) within the above specific numerical ranges (preferably, further having a surface shape having Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) within the above specific numerical ranges). Thus, since it becomes easier to satisfy the above surface shape due to the formation of wrinkles, a matting effect is stably exhibited and a rough touch is also exhibited due to the formation of wrinkles. Regarding wrinkles, from the viewpoint of expressing the above surface shape, improving the matte effect, and improving the rough touch, at least one surface of the transfer layer preferably has an uneven shape composed of irregular wrinkles. The irregular wrinkles are preferably composed of a plurality of convex portions formed by a plurality of protrusions and concave portions formed by being surrounded by the plurality of protrusions. The protrusions preferably have linear protrusions. In this specification, the "linear protrusion" (hereinafter also referred to as "linear protrusion") means that the ratio of the length to the width (length / width) of the protrusion is 3 or more, preferably 5 or more, more preferably 10 or more. The method for determining the length and width is as described below. In this embodiment, a more preferable irregular wrinkle is composed of a plurality of convex portions formed by a plurality of linear protrusions and concave portions formed by being surrounded by the plurality of linear protrusions.

[0026] Examples of these wrinkle-related aspects include the aspect shown in FIG. 5. In FIG. 5, the surface of the transfer layer has irregular wrinkles in a plan view. The irregular wrinkles are composed of a plurality of convex portions 3 formed by a plurality of curved linear protrusions and concave portions 2 formed by being surrounded by the plurality of protrusions (the plurality of convex portions 3). At least a part of the plurality of curved convex portions 3 is formed by meandering linear protrusions, and meandering concave portions 2 are formed so as to be surrounded by the meandering linear protrusions. The transfer layer constituting the transfer sheet of this embodiment stably exhibits a matte effect and a rough touch due to the wrinkles shown in FIG. 5.

[0027] Here, "curvature" means having at least one portion in which the extending direction of the convex portion 3 of the continuous line reverses from one side to the other side in a plan view. Examples of the portion where the extending direction reverses from one side to the other side include, for example, a form having an inflection point when approximated by a continuous curve when the width of the planar shape of the convex portion 3 of the line is ignored (when the width is regarded as 0). Also, when approximated by a straight line when the width of the planar shape of the convex portion 3 of the line is ignored, examples include a form having a V-shaped broken line or a portion approximated by two sides sandwiching one vertex of a triangle. Also, "meandering" means having at least two or more portions in which the extending direction of the convex portion 3 of the continuous line reverses from one side to the other side (hereinafter, also referred to as "reversing portions") in a plan view, and when advancing along the extending direction of the convex portion 3 of the line, having portions where the extending direction of the convex portion 3 of the line alternately reverses in the two adjacent portions. For example, when approximated by a continuous curve when the width of the planar shape of the convex portion 3 of the line is ignored, examples include a form having a portion approximated by the Roman letter "S". Also, when approximated by a straight line when the width of the planar shape of the convex portion 3 of the line is ignored, examples include a form having a portion approximated by the Roman letter "W".

[0028] In this specification, "irregular" means not having a certain rule in shape or being arranged according to a certain rule, that is, not being a so-called patterned shape. Typical examples of non-irregular shapes (regular shapes) include, for example, a shape arranged with a certain periodicity in a specific direction, such as a so-called " lenticular lens" in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction. Therefore, the irregular wrinkles in this embodiment include that the shape of each protrusion itself is irregular and not formed according to a certain rule such as periodicity, and the shapes of the plurality of convex portions formed by the plurality of protrusions are not formed and arranged according to a certain rule and are irregular, and the shape of the concave portion surrounded by such a plurality of protrusions is also irregular. In the transfer layer that constitutes the transfer sheet of the present embodiment, if any of the shape of a single protrusion (a single convex portion), the shape and arrangement of each of the plurality of protrusions (a plurality of convex portions), and the shape of the concave portion surrounded by the plurality of protrusions is irregular, a dulling effect due to having irregular wrinkles and a rough touch can be obtained, but it is preferable that all of them are irregular. The transfer sheet of the present embodiment has irregular wrinkles on the surface of the transfer layer, so that the visibility and texture of the dulling effect are improved, an extremely excellent dulling effect is stably exhibited, and a rough touch is exhibited.

[0029] As described above, the transfer layer has wrinkles, that is, an uneven shape, on at least one of its surfaces. The convex portion and the concave portion in the uneven shape are defined with reference to the median value of the height distribution in the uneven shape, the region with a height exceeding the median value being the convex portion, and the region with a height equal to or less than the median value being the concave portion. For example, using the density difference (i.e., brightness difference) of an image having a density corresponding to the height of the surface of the transfer layer of the present embodiment, the darkest portion in the density distribution image is set to gradation 255, and the lightest portion in the density distribution image is set to gradation 0 (the median value of the density corresponding to the median value of the height is 127). For gradations 0 to 255, gradations 0 to 127 are the concave portions, and gradations 128 to 255 are the convex portions, and they may be classified by binarization processing. The image may be taken after transferring the transfer layer to the adherend.

[0030] It is preferable that irregular wrinkles are formed on at least a part of the surface of the transfer layer of the present embodiment, and it is more preferable that irregular wrinkles are formed over the entire surface. The location where the wrinkles are formed is not particularly limited as long as it is the surface of the transfer layer. For example, it is not limited to only the location corresponding to the decorative layer described later. As long as it is at least a part of the transfer layer surface, the dulling effect and the rough touch due to the formation of wrinkles are exhibited. Also, as shown in FIG. 5, it preferably has a plurality of convex portions formed by a plurality of protrusions having a certain degree of homogeneity although irregular, and a concave portion surrounded by the convex portions. Therefore, in one convex portion (protrusion), a shape in which its width changes extremely is unlikely to become the above surface shape, and it is not a preferable aspect in terms of the visibility and texture of the matte effect, nor is it a preferable aspect in terms of obtaining a rough touch. Regarding the shapes of the convex portions (protrusions) and concave portions that form irregular wrinkles, specific aspects that can be advantageous in stably improving the matte effect and improving the rough touch will be described below. When the wrinkles have the following shapes, it becomes easier to exhibit the above surface shape, and the matte effect and the rough touch are improved.

[0031] Regarding the shape of the wrinkles formed on at least one surface of the transfer layer, the height of the convex portion (height of the protrusion) is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. Also, the width of the convex portion is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less. When the height and width of the convex portion are within the above ranges, it becomes easier to exhibit the above surface shape, and in relation to the concave portion, the matte effect is stably improved, and the rough touch is improved. Here, the above dimensions of the convex portion are the average values of any 10 convex portions (protrusions), that is, a total of 100 convex portions, in any 10 locations (10 regions of 100 μm square) of the transfer sheet of the present embodiment. Also, as shown in FIG. 5, since the width of one convex portion (protrusion) is not the same and varies in width, the width of one convex portion (protrusion) is the average value of the widths of any 5 locations in the one convex portion (protrusion). The same applies to the height of the convex portion (protrusion).

[0032] The depth of the recess is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. Also, the width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less. When the depth and width of the recess are within the above ranges, it becomes easier to exhibit the above surface shape, and in relation to the convex portion, the matting effect is stably improved, and the rough touch is improved. Here, the dimensions of the recess are determined in the same manner as the dimensions of the convex portion described above.

[0033] The distance from the top of the convex portion to the bottom of the recess (the height difference between the convex portion and the recess) is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 8 μm or less, still more preferably 7 μm or less. When the distance is within the above range, it becomes easier to exhibit the above surface shape, the matting effect is stably improved, and the rough touch is improved. Here, the dimensions of the recess are determined in the same manner as the dimensions of the convex portion described above.

[0034] The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, still more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less. When the occupancy ratio of the convex portion is within the above range, it becomes easier to exhibit the above surface shape, and in relation to the occupancy ratio of the recess surrounded by the convex portion, the matting effect is stably improved, and the rough touch is improved. Here, the occupancy ratio of the convex portion is the average value of the occupancy ratios of the convex portions in any 10 locations (10 regions of 100 μm square × 10 locations) of the transfer sheet of the present embodiment.

[0035] The convex and concave portions may have portions with substantially the same direction and substantially the same width. However, from the viewpoint of improving the matting effect and improving the rough touch, it is preferable that their length is short. Specifically, the length in which the convex and concave portions having substantially the same direction and substantially the same width are continuous is preferably 95 μm or less, more preferably 80 μm or less, still more preferably 70 μm or less, and preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more as the lower limit. When the length is within the above range, the wrinkles become more irregular, so that the matting effect is stably improved and the rough touch is improved. Here, for any 10 convex and concave portions (that is, a total of 100 convex and concave portions) in any 10 locations (100 μm square regions × 10 locations) of the transfer sheet of the present embodiment, it is preferable that 80% or more of them satisfy the above conditions, more preferably 85% or more, still more preferably 90% or more, and even more preferably 95% or more. In addition, "substantially" in "substantially the same" in this specification means being generally the same, meaning a difference within ±3° in the case of direction without branching, and a difference within ±5% in the case of width.

[0036] Also, the number of convex portions (protrusions) in a 100 μm square region is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and preferably 200 or less, more preferably 100 or less, still more preferably 70 or less as the upper limit. When the number of the convex portions is within the above range, the matting effect is stably improved and the rough touch is improved. The number of the convex portions is the average value of the number of convex portions in 10 locations (100 μm square regions × 10 locations) of the transfer sheet of the present embodiment.

[0037] FIG. 4 is a cross-sectional view showing an embodiment of the transfer layer 20 constituting the transfer sheet of the present embodiment, and is a cross-sectional view obtained by cutting the transfer layer with a plane parallel to its thickness direction (the Z direction in the figure). As the shape of the concave portion, for example, it may be an acute-angled shape as shown in 2a of FIG. 4, or it may be a semi-circular or semi-elliptical shape as shown in 2b, or a combination of these. Also, a shape such as 2c of FIG. 4 in which one convex portion has a concave portion in part may be used. On the other hand, as the shape of the convex portion, although there are differences in width as shown in 3a and 3b of FIG. 4, it exhibits a semi-circular or semi-elliptical shape.

[0038] Regarding the surface shape of the transfer layer, in order to satisfy the preferable ranges of Ssk (skewness), Sku (kurtosis), Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness), it is preferable to design the surface shape of the release support. This is because the surface shape of the transfer layer becomes a shape that reflects the surface shape of the release support. Among the above parameters, the sign of the value of Ssk (skewness) is reversed between the value of the release support and the value of the transfer layer. For example, when the Ssk (skewness) of the release support is -1.06, the Ssk (skewness) of the transfer layer is 1.06. Among the above parameters, except for Ssk (skewness), the values of the release support and the transfer layer are basically the same. Considering the above points, it is preferable to adjust the surface shape of the release support.

[0039] The surface shape 1 of the article becomes a surface shape complementary to the shape 1 when it is inverted once. And when the complementary surface shape is inverted, it returns to the same surface shape as the surface shape 1 (note that the above "same" is not limited to complete identity, but means identity allowing some error). That is, the surface shape of the article returns to the original surface shape when it is inverted twice. Therefore, first, it is preferable to prepare a basic matte layer, and then, use as the surface shape of the release support a surface shape obtained by inverting the surface shape of the matte layer. A release support having a surface shape obtained by inverting the surface shape of the basic matte layer can be manufactured, for example, by the following steps (1-1) to (1-2), (2-1) to (2-3), (3-1) to (3-2).

[0040] Produce a basic dulling layer 1 that satisfies parameters such as Ssk and Sku. (1-2) Press the dulling layer 1 against the surface of the release support, and impart a shape that is the reverse of the surface shape of the dulling layer 1 to the surface of the release support. As the release support, a laminate having a release layer on a support is used. When pressing the dulling layer 1 against the surface of the release layer, if the release layer is in an uncured state, a shape that is the reverse of the surface shape of the dulling layer 1 can be imparted to the surface of the release layer (= the surface of the release support).

[0041] Produce a basic dulling layer 1 that satisfies parameters such as Ssk and Sku. (2-2) Produce a mold 1 having the same surface shape as the dulling layer 1. The mold 1 having the same surface shape as the dulling layer 1 can be obtained, for example, by producing a mold 2 with the surface shape of the dulling layer 1 reversed, and then producing a mold with the surface shape of the mold 2 reversed. The mold with the surface shape of the mold 2 reversed is the mold 1. The mold 1 and the mold 2 can be produced by a general mold production method such as electroforming. (2-3) Press the mold 1 against the surface of the release support, and impart a shape that is the reverse of the surface shape of the mold 1 (= the surface shape of the dulling layer 1) to the surface of the release support. As the release support, a laminate having a release layer on a support is used. When pressing the mold 1 against the surface of the release layer, if the release layer is in an uncured state, a shape that is the reverse of the surface shape of the mold 1 (= the surface shape of the dulling layer 1) can be imparted to the surface of the release layer (= the surface of the release support).

[0042] (3-1) Design a surface shape that satisfies parameters such as Ssk and Sku by simulation, and produce a mold 3 that reproduces the designed surface shape by laser microfabrication. (3-2) The mold 3 is pressed against the surface of the mold-releasing support, and a shape obtained by inverting the surface shape of the mold 3 (= a surface shape satisfying parameters such as Ssk and Sku) is imparted to the surface of the mold-releasing support. As the mold-releasing support, a laminate having a mold-releasing layer on a support is used. When the mold 3 is pressed against the surface of the mold-releasing layer, if the mold-releasing layer is in an uncured state, a shape obtained by inverting the surface shape of the mold 3 (= a surface shape satisfying parameters such as Ssk and Sku) can be imparted to the surface of the mold-releasing layer (= the surface of the mold-releasing support).

[0043] Also, as described above, the surface shape 1 of the article becomes a surface shape complementary to the shape 1 when it is inverted once. Therefore, the mold-releasing support of the present embodiment can also be manufactured by the following steps (4-1) to (4-3). (4-1) A matte layer 2 having a surface shape obtained by inverting a surface shape satisfying parameters such as Ssk is produced. (4-2) A mold 4 having a surface shape obtained by inverting the surface shape of the matte layer 2 is produced. The surface shape of the mold 4 is a surface shape satisfying parameters such as Ssk. The mold 4 can be produced by a general method for producing a mold such as electroforming. (4-3) The mold 4 is pressed against the surface of the mold-releasing support, and a shape obtained by inverting the surface shape of the mold 4 (= the surface shape obtained by inverting the surface shape of the matte layer 2 = a surface shape satisfying parameters such as Ssk) is imparted to the surface of the mold-releasing support. As the mold-releasing support, a laminate having a mold-releasing layer on a support is used. When the mold 4 is pressed against the surface of the mold-releasing layer, if the mold-releasing layer is in an uncured state, a shape obtained by inverting the surface shape of the mold 4 (= the surface shape obtained by inverting the surface shape of the matte layer 2 = a surface shape satisfying parameters such as Ssk) can be imparted to the surface of the mold-releasing layer (= the surface of the mold-releasing support).

[0044] Furthermore, by the following steps (5-1) to (5-2), a surface shape obtained by directly inverting the desired transfer layer surface shape can be formed on the surface of the mold-releasing layer of the mold-releasing support. (5-1) When producing the mold-releasing support, a layer of an uncured ultraviolet curable resin composition for forming a mold-releasing layer is appropriately formed on the support by a coating method. (5-2) For the layer of the uncured ultraviolet curable resin composition, short wavelength ultraviolet rays are irradiated from an excimer lamp or the like to cure the resin composition, thereby forming a release layer and forming minute wrinkle structures on the surface. At this time, by adjusting the composition of the resin composition and / or the irradiation conditions of the short wavelength ultraviolet rays, a shape obtained by inverting a desired surface shape to be formed on the surface of the transfer layer can be formed on the surface of the release layer.

[0045] 〔Base matting layer〕 The base matting layer (1) It is preferable to form minute wrinkle structures on the surface of the matting layer. This is preferable. Furthermore, the base matting layer (2) Optimize the composition formulation of the resin composition for forming the matting layer, particularly the types, number of functional groups, molecular weight, presence or absence of a wrinkle forming stabilizer, and when using a wrinkle forming stabilizer, the particle size and content of the wrinkle forming agent. (3) Optimize the irradiation conditions of the resin composition for forming the matting layer, particularly the wavelength, integrated light quantity, ultraviolet output density, etc. of light with a wavelength of 100 nm or more and 380 nm or less that can cause curing shrinkage of the surface portion of the matting layer. (4) In addition to the above, it is preferable to optimize the type and thickness of the base material for forming the matting layer, the thickness of the matting layer, etc. This is preferable. By optimizing these, for the surface shape of the base matting layer (= the surface shape of the transfer layer in this embodiment), Ssk (skewness) and Sku (kurtosis) are within the above specific numerical ranges, and preferably Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) described later are easily within a predetermined numerical range.

[0046] The base material for forming the basic dulling layer can be used without particular limitation and can be appropriately selected according to desired properties and the like. From the viewpoints of improving the dulling effect and the rough touch, a base material composed of a resin and a base material composed of a fibrous material are preferable. Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable, olefin resins and polyester resins are more preferable, and polypropylene is even more preferable. Among fibrous materials, paper is preferable. By using a base material composed of these materials, the above surface shape can be particularly easily obtained, and the rough touch can be easily improved.

[0047] The basic dulling layer is preferably a layer composed of a cured product of a resin composition, preferably a cured product of a curable resin composition containing a cured resin.

[0048] As the resin composition for forming the dulling layer, from the viewpoint of obtaining a dulling layer having an excellent dulling effect and excellent in rough touch, a resin composition containing a resin and a wrinkle formation stabilizer (hereinafter sometimes referred to as "resin composition for forming a dulling layer") is preferable. That is, the dulling layer is preferably a layer containing a resin and a wrinkle formation stabilizer.

[0049] (Wrinkle formation stabilizer) The wrinkle formation stabilizer has a function of imparting a stable dulling effect visibility (hereinafter sometimes simply referred to as "stable dulling effect visibility", and expressions equivalent thereto may be used) in which the visibility of the dulling effect is uniformly exhibited over the entire surface of the dulling layer and partial unevenness of gloss is reduced by stabilizing the formation of wrinkles on at least one surface of the dulling layer, and the uniformity of the surface state (also referred to as "texture"). And the wrinkles formed in the dulling layer also greatly contribute to the expression of a rough touch. Therefore, even if the so-called "matting agent" in the prior art and the "wrinkle-forming stabilizer" in the present embodiment have the same constituent materials and average particle diameters, their matting mechanisms (actions), structures for expressing matting, and relationships between the usage amounts and the degree of surface gloss (gloss value) are different. Also, in terms of expressing a rough touch by forming wrinkles, it is different from the "matting agent".

[0050] In the prior art such as the above Patent Document 1, the matting agent used for matting expression exhibits the visibility of the matting effect due to the light diffusion effect caused by the physical shape. Specifically, what is generally called a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and exhibits the visibility of the matting effect due to the light reflection corresponding to the contour shape of the particles and the light diffusion effect by the refractive interface. On the other hand, the wrinkle-forming stabilizer of the present embodiment does not exhibit the visibility of the matting effect by light reflection and refraction by the particles themselves, but rather stabilizes the formation of wrinkles on the surface of the matting layer due to the wrinkle-forming stabilizer, and thereby stably imparts a texture along with the visibility of the matting effect to the matting layer by the light diffusion effect at the refractive index difference interface between such a surface and air. Therefore, the wrinkle-forming stabilizer used in the present embodiment is different from the matting agent that exhibits the visibility of the matting effect by itself (even if their constituent materials and average particle diameters are the same), in terms of their matting mechanisms (actions), structures for expressing matting, etc. Furthermore, the "wrinkle-forming stabilizer" and the "matting agent" are also different in terms of the relationship between the content and the surface gloss (gloss value). When the same substance A is used as a wrinkle-forming initiator AW (W: wrinkle), and a specific amount C of this is contained to form wrinkles on the surface, the 60° gloss value G 60° AW (C) of the surface is lower than the 60° gloss value G 60° AM (C) of the surface when the same substance A is used simply as a matting agent AM and contained in the specific amount C without forming wrinkles on the surface. That is, the following relational expression holds. G 60°AW (C)<G 60° AM (C)

[0051] The matting layer may contain an agent that has been conventionally used as a matting agent, but preferably does not contain a matting agent. Thus, it can be said that the matting layer of the present embodiment has extremely excellent visibility and texture of the matting effect even if it does not substantially contain the matting agent that has been used to obtain the visibility of the conventional matting effect. Here, "not containing a matting agent" means that in addition to not containing any matting agent, even if it contains, it does not have the visibility of the matting effect based on the action effect of the matting agent itself. Specifically, it means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, more preferably 3.0 parts by mass or less with respect to 100 parts by mass of the resin. In the present specification, the "matting agent" specifically means particles having an average particle diameter with a lower limit being the smaller of either more than 100% and more than 30 μm of the thickness of the matting layer, that is, the layer in which the matting agent can be contained, from the viewpoint of forming convex portions by the blooming effect as described above.

[0052] In the present embodiment, as the wrinkle formation stabilizer, any one can be used without particular limitation as long as it is not a matting agent and has an average particle diameter with an upper limit being the smaller of either 100% or less and 30 μm or less of the thickness of the matting layer. From the perspective of improving the matting effect and the rough touch, it is preferable to use at least one of two types of wrinkle-forming stabilizers distinguished by their average particle size, with the upper limit being the smaller of 100% or less of the thickness of the matting layer and 30 μm or less. Specifically, the two types of wrinkle-forming stabilizers are a wrinkle-forming stabilizer 1 with an average particle size of 1 μm or more and the upper limit being the smaller of 100% or less of the thickness of the matting layer and 30 μm or less, and a wrinkle-forming stabilizer 2 with an average particle size of less than 1 μm. In this embodiment, if at least one of the two types of wrinkle-forming stabilizers is used, the formation of wrinkles is stable, a stable and excellent matting effect can be obtained, and a rough touch can also be obtained. In this embodiment, the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 can be used alone or in combination. From the perspective of improving the matting effect and the rough touch, it is more preferable to use the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 in combination.

[0053] As the wrinkle-forming stabilizer, for example, organic particles and inorganic particles can be used. Examples of the organic substances constituting the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin, and polyester resin. Examples of the inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate. Among these, silica with excellent transparency is preferable.

[0054] The shape of the wrinkle-forming stabilizer is not particularly limited, and examples include spherical, polyhedral, scaly, and amorphous.

[0055] The average particle size of the wrinkle formation stabilizer 1 is 1 μm or more, and is capped at the smaller of 100% or less and 30 μm of the thickness of the matting layer. From the perspective of stably improving the matting effect and improving the rough touch, the average particle size of the wrinkle formation stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, still more preferably 1.8 μm or more. As the upper limit, with respect to the thickness of the matting layer, it is preferably 90% or less of the thickness of the matting layer, more preferably 80% or less of the thickness of the matting layer, still more preferably 70% or less of the thickness of the matting layer. In terms of the absolute value, it is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, even more preferably 7 μm or less. It suffices to take the smaller of any arbitrary combination of the upper limit with respect to the thickness of the matting layer and the upper limit of the absolute value. For example, the upper limit may be the smaller of 90% or less and 20 μm of the thickness of the matting layer, or the upper limit may be the smaller of 90% or less and 10 μm of the thickness of the matting layer. Note that the thickness of the matting layer will be described later.

[0056] Also, the average particle size of the wrinkle formation stabilizer 2 is less than 1 μm. From the perspective of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the rough touch, the average particle size of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, still 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 the particle size distribution measurement by the laser light diffraction method.

[0057] From the viewpoint of stabilizing the formation of wrinkles by the wrinkle-forming stabilizer, stably improving the matting effect, and improving the rough touch, the content of the wrinkle-forming stabilizer (when the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 are used in combination, the total content thereof) is preferably 0.5 part by mass or more, more preferably 0.75 part by mass or more, still more preferably 1.0 part by mass or more, even more preferably 1.2 part by mass or more, based on 100 parts by mass of the resin forming the matting layer. As the upper limit, there is no particular limitation from the viewpoint of stably improving the matting effect and improving the rough touch. However, for example, from the viewpoint of the productivity of the cosmetic material due to the coatability of the resin composition for forming the matting layer, etc., and efficiently improving the visibility and texture of the matting effect, it is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, still more preferably 10.0 parts by mass or less, even more preferably 7.5 parts by mass or less, and particularly preferably 6.0 parts by mass or less.

[0058] When the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 are used in combination, the content of each of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is not particularly limited as long as the total content is within the above range. However, the content of the wrinkle-forming stabilizer 2 is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1.0 part by mass or more, based on 100 parts by mass of the resin. As the upper limit, it is preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, still more preferably 5.0 parts by mass or less, even more preferably 3.5 parts by mass or less. Further, the blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 0.05 to 0.95 part by mass, more preferably 0.10 to 0.90 part by mass, still more preferably 0.20 to 0.80 part by mass, even more preferably 0.30 to 0.70 part by mass, as the blending amount of the wrinkle-forming stabilizer 1 when the total amount thereof is 100 parts by mass.

[0059] As the wrinkle-forming stabilizer, as described above, organic particles and inorganic particles can be used. However, it can be said that the types of these particles themselves include those that are also conventionally used as matting agents. For example, in the matting layer of the cosmetic sheet described in Patent Document 1 above, matting agents such as spherical alumina and calcium carbonate are used. In order for matting agents such as spherical alumina and calcium carbonate to exhibit the visibility of the matting effect due to the light diffusion effect caused by their physical shape, as described in Patent Document 1, it is necessary to use them at a content of about 50 parts by weight in total, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, per 100 parts by weight of the resin component. However, in the present embodiment, as described above, even with a small content, that is, even with a content less than the content required for the matting agent itself to exhibit the visibility of the matting effect due to the light diffusion effect caused by its physical shape, a matting effect extremely superior to the effect obtained by the matting agent is obtained, and furthermore, a rough touch is also obtained. Therefore, it can be said that the matting layer of the present embodiment, although substantially free of a matting agent, stably forms wrinkles on the surface, so that the visibility of a matting effect more excellent than when using a matting agent is stably obtained, and at the same time, a texture is obtained, and furthermore, a rough touch is also obtained.

[0060] (Resin) As the resin for forming the matting layer, any resin may be used as long as it forms a resin composition for forming a matting layer containing a predetermined amount of the above wrinkle-forming stabilizer and is cured to form a cured product that constitutes the matting layer. Examples of such a resin include radiation-curable resins. As described above, when the matting layer itself is used as a shaping sheet (1-2 above), a mold may be manufactured based on the matting layer (2-2 above). For this reason, the resin for forming the matting layer is preferably a resin that easily exhibits surface properties such as processing characteristics and scratch resistance, and radiation-curable resins are preferable resins from these viewpoints. Since the content of the wrinkle-forming stabilizer contained in the matting layer of the present embodiment is extremely small, as its surface property, the performance of the resin for forming the matting layer is more directly exhibited.

[0061] The radiation-curable resin is a resin having a radiation-curable functional group. The radiation-curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation. Preferred examples thereof include functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group, allyl group, etc. In the present specification, the (meth)acryloyl group means an acryloyl group or a methacryloyl group. Further, in the present specification, (meth)acrylate means acrylate or methacrylate. Also, ionizing radiation means those having energy quanta capable of polymerizing and / or crosslinking molecules among electromagnetic waves or charged particle beams. Usually, ultraviolet rays (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays, γ-rays, and charged particle beams such as α-rays and ion beams are also included.

[0062] Examples of the radiation-curable resin include electron beam-curable resins and ultraviolet ray-curable resins. From the viewpoints of stabilizing the formation of wrinkles by a wrinkle-forming stabilizer and stably improving the matting effect and improving the rough touch, an ultraviolet ray-curable resin is preferred. Specifically, the radiation-curable resin can be appropriately selected and used from conventionally used polymerizable monomers and polymerizable oligomers as radiation-curable resins.

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

[0064] From the viewpoints of stabilizing the formation of wrinkles, stably improving the matting effect, improving the rough touch, and further improving surface properties such as post-processing characteristics, scratch resistance, and weather resistance, the number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, still more preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less. Also, when the number of functional groups is as described above, the above surface shape is particularly likely to be obtained, and it becomes easier to improve the rough touch. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

[0065] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group. For example, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, etc. can be mentioned. Furthermore, examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate oligomers having a (meth)acrylate group in the side chain of a polybutadiene oligomer, silicone (meth)acrylate oligomers having a polysiloxane bond in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying an aminoplast resin having many reactive groups in a small molecule, and oligomers having a cationic polymerizable functional group in the molecule such as novolak type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0066] These polymerizable oligomers may be used alone or in combination of two or more. From the viewpoints of stabilizing the formation of wrinkles, steadily improving the matting effect, improving the rough touch, and further improving surface properties such as post-processing characteristics, scratch resistance, and weather resistance, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, and acrylic (meth)acrylate oligomer are preferred, urethane (meth)acrylate oligomer and polycarbonate (meth)acrylate oligomer are more preferred, and urethane (meth)acrylate oligomer is even more preferred.

[0067] From the viewpoints of stabilizing the formation of wrinkles, steadily improving the matting effect, improving the rough touch, and further improving surface properties such as processing characteristics, scratch resistance, and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, more preferably 6 or less as the upper limit, and even more preferably 4 or less. Also, from the same viewpoints, the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and even more preferably 3,500 or more and 6,000 or less. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

[0068] In this embodiment, as the resin for forming the matte layer, the above-mentioned polymerizable oligomer can be used alone, the above-mentioned polymerizable monomer can be used alone, or the above-mentioned polymerizable oligomer and polymerizable monomer can be used in combination. However, it is preferable to use the above-mentioned polymerizable monomer alone or in combination of the above-mentioned polymerizable oligomer and polymerizable monomer. As the polymerizable oligomer, a polyfunctional urethane (meth) acrylate oligomer is preferable, a polyfunctional urethane acrylate oligomer is more preferable. As the polymerizable monomer, a polyfunctional polymerizable monomer is preferable, a polyfunctional (meth) acrylate monomer is more preferable, and a polyfunctional acrylate monomer is still more preferable. It is possible to stabilize the formation of wrinkles, stably improve the matte effect, improve the rough touch, and further improve surface properties such as processing characteristics, scratch resistance, and weather resistance. When used in combination, from the same viewpoint, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more, 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, still more preferably 70 parts by mass or less.

[0069] (Resin composition) The matte layer is preferably composed of a cured product of a resin composition containing the above-mentioned wrinkle formation stabilizer in a predetermined content, and the resin composition preferably contains the above-mentioned resin and the wrinkle formation stabilizer in a predetermined content. The resin composition used in this embodiment may contain other components according to desired performances and the like in addition to the above-mentioned wrinkle formation stabilizer and resin. The resin composition for forming the matte layer may contain a monofunctional (meth) acrylate for the purpose of, for example, reducing its viscosity. These monofunctional (meth) acrylates may be used alone or in combination of plural kinds.

[0070] When the resin is an ultraviolet curable resin that cures by ultraviolet rays, it is preferable to contain additives such as a photoinitiator and a photo - polymerization accelerator. By containing these additives, the resin can be cured using ultraviolet rays (without using ionizing radiation), and surface characteristics useful for practical applications can be obtained. Examples of the photoinitiator include one or more selected from acetophenone, benzophenone, α - hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethyl ketal, benzoyl benzoate, α - acyloxime ester, thioxanthones, etc. In addition, the photo - polymerization accelerator can reduce the polymerization inhibition by air during curing and increase the curing rate. For example, one or more selected from isoamyl p - dimethylaminobenzoate, ethyl p - dimethylaminobenzoate, etc. can be mentioned.

[0071] (Method for forming a matte layer) The first method for forming the matte layer of the present embodiment includes a matte layer forming step of forming a layer of a resin composition for forming a matte layer containing the above - mentioned resin and a wrinkle - forming stabilizer by irradiating with light having a wavelength of at least 100 nm or more and 380 nm or less. By the first forming method, a matte layer having a surface shape as shown in FIG. 4, for example, can be formed (the transfer layer in FIG. 4 is obtained by inverting the surface shape of the matte layer twice. That is, the surface shape of the transfer layer in FIG. 4 is the same as the surface shape of the matte layer). For example, if the above - mentioned resin composition for forming a matte layer is applied onto a substrate, a layer of the resin composition is formed on the substrate, and the matte layer is formed by irradiating with the above - mentioned wavelength light, a laminate having a substrate and a matte layer can be manufactured. This forming method is suitable for forming a matte layer having a matte effect with a 60° gloss value on the matte layer side of 20.0 or less, 10.0 or less, and even lower, and having a rough touch.

[0072] By the method for forming a matte layer according to this embodiment, it becomes possible to easily obtain a basic matte layer. Specifically, when forming the matte layer, ultraviolet rays with a short wavelength of at least 100 nm or more and 380 nm or less are irradiated onto a resin composition for forming a matte layer containing a wrinkle-forming stabilizer for forming the matte layer, whereby wrinkles can be formed on at least one surface of the matte layer, and it becomes possible to impart a matte effect and a rough touch to the matte layer.

[0073] Although the details of the mechanism by which such short-wavelength ultraviolet rays are irradiated onto the resin composition for forming a matte layer to form wrinkles and exhibit a matte effect and a rough touch on at least one surface of the matte layer are unknown, it is presumed to be due to the following mechanism.

[0074] When short-wavelength ultraviolet rays are irradiated onto a coating layer obtained by coating a resin composition for forming a matte layer with a predetermined thickness, the energy of the ultraviolet rays penetrates only the surface portion, and the energy does not reach the lower layer. Therefore, only the surface portion of the resin composition starts to cure, and it is considered that wrinkles are formed by the occurrence of curing shrinkage only on the surface. Thus, it is considered that the formation of wrinkles occurs in a state where only a certain thickness direction from the surface of the resin composition for forming a matte layer is cured by irradiation with short-wavelength ultraviolet rays. Further, from the comparison between the examples and comparative examples described below, when the wrinkle-forming stabilizer is not included, the formation of wrinkles becomes unstable, and the visibility and texture of the matting effect are not stably and sufficiently expressed over the entire surface of the matting layer, and the rough touch is not sufficiently expressed. Therefore, the stable expression of the matting effect and the rough touch cannot be explained only by the curing of only the surface portion by ultraviolet rays of short wavelengths. That is, in order for the matting layer of the present embodiment to stably have wrinkles and exhibit the matting effect and the rough touch, it is essential to include a wrinkle-forming stabilizer. Considering that a stable matting effect and a rough touch due to the formation of wrinkles are not obtained when the wrinkle-forming stabilizer is not included, the wrinkle-forming stabilizer has a function like a nucleus that triggers the formation of wrinkles. Centering around the nucleus, the resin on the surface portion of the resin composition gathers to form the convex portions (protrusions) of the wrinkles, and concave portions are formed along with the formation of the convex portions (protrusions). As a result, the formation of wrinkles is stabilized, and it is considered that the matting effect and the rough touch are stably expressed.

[0075] In the forming method of the present embodiment, the resin composition for forming the matting layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. By this irradiation, as described above, the energy of the ultraviolet rays penetrates only the surface portion, and the energy does not reach the lower layer. Therefore, only the surface portion of the resin composition starts to cure, and wrinkles are stably formed by the curing shrinkage occurring only on the surface. The surface layer of the resin composition becomes a cured product and constitutes the matting layer. Then, after that, the curing proceeds from the vicinity of the surface where the progress of curing is slow to the deep portion away from the surface in the depth direction, and the layer of the resin composition becomes a cured product, so that the entire thickness of the resin composition is cured, and a matting layer having a light diffusion effect on the surface and wrinkles exhibiting a rough touch is constituted. From the viewpoint of promoting the progress of curing in the deep portion, as described below, 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.

[0076] As the light with a wavelength of at least 100 nm and at most 380 nm, for example, "excimer light" including ultraviolet light in the wavelength range from an excited dimer, that is, an excimer, formed by the discharge of a noble gas such as Ar, Kr, Xe, Ne, a halide of a noble gas by a halogen such as F, Cl, I, Br, or a mixed gas of these is preferable. As the wavelength of the excimer light and the excimer serving as the light source, for example, light with a wavelength of 126 nm radiated from an 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), 351 nm (XeF), etc. can be preferably adopted. As the excimer light, either spontaneous emission light or laser light with high coherence (interferability) by induced emission can be used, but usually, spontaneous emission light is sufficient. Note that the discharge lamp that emits the light (ultraviolet light) is also referred to as an "excimer lamp". The excimer light is characterized in that it has a single wavelength peak and a narrow half-value width of the wavelength compared with ordinary ultraviolet light (for example, ultraviolet light radiated from a metal halide lamp, a mercury lamp, etc.). By using such excimer light, the formation of wrinkles is stabilized, the matting effect is stably improved, and the rough touch is also improved.

[0077] From the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the rough touch, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, even more preferably 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, even more preferably less than 200 nm, and most preferably 172 nm (Xe2). Thus, in the present embodiment, from the viewpoint of stably improving the matting effect and improving the rough touch, it is preferable to use light having a shorter wavelength, and medium wavelength ultraviolet rays (wavelength: 280 to 320 nm) and short wavelength ultraviolet rays (wavelength: 280 nm or less) are more preferable, and short wavelength ultraviolet rays are even more preferable. The short wavelength ultraviolet rays preferably have a wavelength in a region of less than 200 nm.

[0078] In the present embodiment, from the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the rough touch, the integrated light amount of the above wavelength light is preferably 1 mJ / cm 2 or more, more preferably 10 mJ / cm 2 or more, still more preferably 30 mJ / cm 2 or more, even more preferably 50 mJ / cm 2 or more. There is no particular limitation on the upper limit, and from the viewpoint of reducing the number of lamps required for irradiating the wavelength light and improving productivity such as improving production efficiency, the upper limit is preferably 1,000 mJ / cm 2 or less, more preferably 500 mJ / cm 2 or less, still more preferably 300 mJ / cm 2 or less. From the same viewpoint, the ultraviolet output density is preferably 0.001 W / cm or more, more preferably 0.01 W / cm or more, still more preferably 0.03 W / cm or more, and the upper limit is preferably 10 W / cm or less, more preferably 5 W / cm or less, still more preferably 3 W / cm or less. In addition, the oxygen concentration when irradiating the above wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, even more preferably 300 ppm or less.

[0079] In the matting layer forming step of this embodiment, 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 the curing of the resin composition for forming the matting layer may be performed. For example, from the viewpoint of stabilizing the formation of wrinkles due to the difference in the degree of progress of curing between the surface portion described above and the deep portion away from the surface in the depth direction, and promoting the progress of curing in the deep portion, for example, light having a wavelength exceeding 380 nm, preferably light having a wavelength of about 385 nm or more and 400 nm or less may be irradiated in advance to preliminarily cure the entire resin composition for forming the matting layer, and then irradiated with light having a wavelength of 100 nm or more and 380 nm or less. Alternatively, after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed to further cure the resin composition. Whether to employ pre-curing and post-curing may be appropriately determined according to the desired properties (for example, surface properties such as processing characteristics and stain resistance) required for the matting layer. Further, although the above wavelength light belongs to ultraviolet rays, not only ultraviolet rays but also other ionizing radiations such as electron beams can be used. For example, in post-curing, an electron beam can be preferably used from the viewpoint of improving the surface properties of the matting layer.

[0080] In the forming method of this embodiment, the matting layer can be formed by irradiating a coating layer (uncured resin layer) obtained by applying a resin composition for forming the matting layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method with light having a wavelength of at least 100 nm or more and 380 nm or less.

[0081] <Release support> The release support is peeled off from the transfer layer after transferring the transfer layer to the adherend. The surface shape of the release support is a shape obtained by inverting the surface shape of the transfer layer. The release support may have a single-layer structure or a structure of two or more layers. The release support preferably has a configuration in which a release layer is provided on a support.

[0082] 〔Support〕 The material of the support is not particularly limited, and examples include paper, fiber, metal, glass, ceramics, resin, and the like. Among these, a support made of resin is suitable because it is easy to form a release layer and has good releasability after transfer. Hereinafter, a support made of resin is referred to as a plastic film.

[0083] There is no particular limitation on the thickness of the support. That is, the support in the present embodiment may be a support with a thin thickness in micrometers or a support with a thick thickness of millimeter units or more. The support may or may not be colored. Further, when the support is colored, there is no particular limitation on the coloring mode, and it may be transparent coloring or opaque coloring (concealing coloring).

[0084] Examples of the resin constituting the plastic film include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, and various olefin-based thermoplastic elastomers; vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, and polyester-based thermoplastic elastomers; acrylic resins such as poly(meth)acrylate methyl, poly(meth)acrylate ethyl, poly(meth)acrylate butyl, and (meth)acrylate methyl-(meth)acrylate butyl copolymer; polyamide resins represented by nylon 6 or nylon 66; cellulose-based resins such as triacetate cellulose, cellophane, and celluloid; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymer, and acrylonitrile-butadiene-styrene copolymer (ABS); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin. Among these, polyester resins are preferred, and among the polyester resins, polyethylene terephthalate is preferred.

[0085] 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 20 μm or more and 125 μm or less.

[0086] In order to enhance the adhesion to the release layer, the support may be subjected to surface treatment such as physical surface treatment like oxidation method, roughening method, or chemical surface treatment on one or both of its surfaces, or an easy-adhesive layer may be formed.

[0087] [Release layer] The release layer is a layer provided as necessary to improve the peelability between the release support and the transfer layer. In order to improve the peelability with the transfer layer, it is preferably provided over the entire surface of the support. The release layer preferably contains a resin, and more preferably contains a resin and a release agent.

[0088] (Resin) The release layer preferably has a resin as the main component. The main component means 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, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0089] In order to improve the durability, the release layer preferably contains a cured product of a resin composition containing a curable resin as the resin. The proportion of the cured product of the resin composition containing a curable resin with respect to the total amount of the resin contained in the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and most preferably 100% by mass.

[0090] 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 a radiation-curable resin. The cured product of the resin composition containing the radiation-curable resin is preferable in that it is easier to improve the scratch resistance.

[0091] The resin composition containing a thermosetting resin is a composition containing at least a thermosetting resin and is a resin composition that cures by heating. Examples of the thermosetting resin include acrylic resins, urethane resins, urethane acrylate resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, silicone resins, and the like. These can be used alone or in combination of two or more. Further, the resin composition containing a thermosetting resin may be one to which a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent is added.

[0092] Examples of the radiation-curable resin for the release layer include those exemplified as the radiation-curable resin for the matting layer.

[0093] (Release agent) Examples of the release agent include fluorine-based release agents and silicone-based release agents. From the viewpoint of obtaining higher release properties at a lower cost, silicone-based release agents are preferable.

[0094] Examples of the silicone-based release agent include those having a polysiloxane structure as a basic structure. Among them, modified silicone oils having organic groups introduced into at least one of the side chains and terminals are preferable, and modified silicone oils having organic groups introduced into both terminals are more preferable. From the viewpoint of obtaining a more textured design, reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenol groups, and carboxyl groups, and non-reactive group functional groups such as polyether groups, aralkyl groups, fluoroalkyl groups, alkyl groups, fatty acid amide groups, and phenyl groups are preferably mentioned. Among them, reactive functional groups are preferable, and (meth)acrylic groups are particularly preferable, that is, (meth)acrylic-modified silicone oils are particularly preferable. Further, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

[0095] 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 still more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the resin forming the release layer. When the content of the release agent is within the above range, the addition effect of the release agent can be obtained efficiently.

[0096] The surface shape of the release layer is a shape obtained by inverting the surface shape of the transfer layer. Therefore, the release layer preferably 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, still 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, still more preferably 150 μm or less, and even more preferably 100 μm or less. In this specification, the thickness of the release layer is the average value of the thicknesses at 20 locations measured from an image taken using a scanning electron microscope (SEM) for the cross-section of the transfer sheet. 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.

[0097] 〔Other Layers〕 The releasable support constituting the transfer sheet of the present embodiment may have layers other than the support and the release layer. Examples of the layers other than the support and the release layer include an antistatic layer and an easy-adhesion layer.

[0098] <Transfer Layer> The transfer layer is a layer to be transferred to the adherend. The transfer layer preferably has at least a release layer. Further, it is more preferable that the transfer layer has a release layer and an adhesive layer in this order from the side of the releasable support. Furthermore, it is more preferable that the transfer layer has one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer. When having a primer layer and a decorative layer between the release layer and the adhesive layer, it is preferable that the position of the primer layer is closer to the release layer side than the decorative layer.

[0099] In addition, the transfer layer may further have other functional layers. Examples of the other functional layers include an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an anti-fogging layer, and a transparent conductive layer.

[0100] 〔Release layer〕 The release layer is a layer located on the outermost surface of the transfer layer when transferred to the adherend. Therefore, it is preferable that the release layer has good scratch resistance, weather resistance, stain resistance, etc.

[0101] The release layer preferably contains a resin as a main component. The main component means 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, still more preferably 90% by mass or more, and most preferably 100% by mass.

[0102] In order to improve the scratch resistance, the release layer preferably contains a cured product of a resin composition containing a curable resin as the resin. The proportion of the cured product of the resin composition containing a curable resin with respect to the total amount of the resin contained in the release layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and most preferably 100% by mass.

[0103] 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 a radiation curable resin. The cured product of the resin composition containing a thermosetting resin is preferable in terms of being easily able to improve the weather resistance because there is no restriction on the use of an ultraviolet absorber. The cured product of the resin composition containing a radiation curable resin is preferable in terms of being easily able to improve the scratch resistance. Among them, the cured product of the resin composition containing an electron beam curable resin is preferable in terms of being able to improve the scratch resistance and being easily able to improve the weather resistance because there is no restriction on the use of an ultraviolet absorber.

[0104] Examples of the resin composition containing a thermosetting resin of the release layer include those exemplified as the resin composition containing a thermosetting resin of the release layer. Examples of the resin composition containing the ionizing radiation curable resin for the release layer include those exemplified as the resin composition containing the ionizing radiation curable resin for the matting layer, and urethane acrylate resins such as urethane (meth) acrylate oligomers are preferred.

[0105] The release layer may contain particles such as a matting agent and a wrinkle formation stabilizer, but preferably does not substantially contain the particles. By substantially not containing particles in the release layer, it is possible to suppress a decrease in the scratch resistance, weather resistance, stain resistance, etc. of the release layer due to the dropout of the particles. That the release layer substantially does not contain particles means that the content of the particles 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 still more preferably 0% by mass.

[0106] In order to improve the weather resistance, the release layer preferably contains an ultraviolet absorber or a light stabilizer, and more preferably contains both an ultraviolet absorber and a light stabilizer. As the ultraviolet absorber and the light stabilizer, general-purpose compounds can be used. Among the ultraviolet absorbers, hydroxy phenyl triazine compounds are preferred. Among the light stabilizers, hindered amine compounds are preferred.

[0107] The content of the ultraviolet absorber in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and still more preferably 1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the resin of the release layer. The content of the light stabilizer in the release layer is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, and still more preferably 1 part by mass or more and 7 parts by mass or less with respect to 100 parts by mass of the resin of the release layer.

[0108] 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 still 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.

[0109] [Adhesive layer] The release layer is a layer formed as necessary to facilitate the transfer of the transfer layer to the adherend. For example, when transferring the transfer layer of a transfer sheet to an adherend, if a separately prepared adhesive is used between the adherend and the transfer sheet, the transfer layer may not have an adhesive layer. Also, if the transfer layer and the adherend can be adhered without using an adhesive, the transfer layer may not have an adhesive layer. When the transfer layer has an adhesive layer, it is preferable to form the adhesive layer at the position farthest from the release support among the layers constituting the transfer layer. The adhesive layer can also serve as the function of the decorative layer described later.

[0110] Examples of the adhesive layer include a pressure-sensitive adhesive layer, a curable adhesive layer, and a heat-sensitive adhesive layer. Among these, a heat-sensitive adhesive layer is preferable 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 may also be called a heat-seal layer.

[0111] When the adhesive layer is a pressure-sensitive adhesive layer, it is preferable to include an adhesive in the adhesive layer. As the adhesive, adhesives such as acrylic, urethane, silicone, and rubber can be appropriately selected and used.

[0112] When the adhesive layer is a curable adhesive layer, it is preferable to include a thermosetting adhesive in the adhesive layer. As the thermosetting adhesive, those containing a composition having the property of undergoing a chemical reaction and crosslinking by heat are preferable. For example, two-component curable urethane adhesives, polyester urethane adhesives, polyether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, etc. can be exemplified. The urethane resin constituting the two-component curable urethane adhesive is a polyurethane having a polyol (polyhydric alcohol) as the main agent and an isocyanate as the crosslinking agent (curing agent).

[0113] When the adhesive layer is a heat-sensitive adhesive layer, it is preferable that the adhesive layer contains a thermoplastic resin. Examples of the thermoplastic resin 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, epoxy resins, etc. These can be used alone or in combination of multiple types. Among these, acrylic resins with good weather resistance are preferable.

[0114] The weight average molecular weight of the thermoplastic resin is preferably 10,000 or more and 200,000 or less, more preferably 50,000 or more and 150,000 or less, and even more preferably 80,000 or more and 120,000 or less. When the weight average molecular weight of the thermoplastic resin is within the above range, the coating suitability becomes good, and it becomes easy to form the adhesive layer in a good state. Furthermore, when the weight average molecular weight of the thermoplastic resin is within the above range, it is easy to improve the adhesion between the adhesive layer and the adherend.

[0115] The thickness of the adhesive layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and even more preferably 3 μm or more and 7 μm or less. When the thickness of the adhesive layer is within the above range, it is easy to improve the adhesion between the adhesive layer and the adherend, and it is also easy to improve the handleability of the transfer sheet.

[0116] The adhesive layer can contain a colorant as needed. When the adhesive layer contains a colorant, the designability of the transfer layer can be enhanced by the adhesive layer alone or in combination with a decorative layer described later.

[0117] The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, lead yellow, titanium yellow, Indian yellow, cadmium red, ultramarine, cobalt blue, etc.; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, azomethine azo black, etc.; metallic pigments such as flaky foil pieces of aluminum, brass, etc.; pearlescent (pearl) pigments such as flaky foil pieces of titanium dioxide-coated mica, basic lead carbonate, etc.; and the like.

[0118] 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 with respect to 100 parts by mass of the resin constituting the adhesive layer. When the content of the colorant is 5 parts by mass or more, it is easy to improve the design property of the transfer layer. Further, when the content of the colorant is 90 parts by mass or less, it is easy to suppress the decrease in the adhesive strength of the adhesive layer.

[0119] 〔Primer layer〕 In order to improve the adhesion between the layers constituting the transfer layer, the transfer layer may be subjected to surface treatment such as the above-described physical surface treatment or chemical surface treatment on the surface of each layer, or a primer layer may be formed between the layers. The surface treatment and the formation of the primer layer may be both carried out. The primer layer can be formed, for example, between the release layer and the adhesive layer. When the primer layer and the decorative layer are provided between the release layer and the adhesive layer, it is preferable that the position of the primer layer is closer to the release layer side than the decorative layer. When the primer layer is formed between the release layer and the adhesive layer, the interlayer adhesion of the transfer layer becomes good, and the weather resistance and durability of the transfer layer can be improved.

[0120] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer as necessary.

[0121] Examples of the binder resin 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 having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains (polycarbonate polyols)), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), cellulose acetate resins, etc. These can be used alone or in combination of two or more. Further, the binder resin may be a crosslinked and cured product obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins. Among these, polycarbonate-based urethane-acrylic copolymers are preferred.

[0122] 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 preferred in terms of good flexibility, easy follow-up to the curing shrinkage of the release layer, good weather resistance, etc. (1) React polycarbonate diol with (di)isocyanate to obtain a polycarbonate-based polyurethane polymer. (2) Radical polymerize the polycarbonate-based polyurethane polymer and an acrylic monomer to obtain a polycarbonate-based urethane acrylic copolymer.

[0123] 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, o- or p-isocyanatophenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; alicyclic isocyanates; etc.

[0124] Examples of acrylic monomers include (meth)acrylic acid alkyl esters such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0125] The mass ratio of the acrylic component to the urethane component in the polycarbonate-based urethane acrylate copolymer is preferably in the range of 95:5 to 30:70, more preferably in the range of 93:7 to 50:50, and even more preferably in the range of 90:10 to 60:40 in terms of the mass ratio of the urethane component to the acrylic component. By setting the mass ratio of the acrylic component to the urethane component within the above range, the primer layer will not form an overly hard coating film, and sufficient processability can be obtained. Also, when the peeling layer is made of a urethane acrylic resin such as urethane (meth)acrylate oligomer, the interlayer adhesion with the peeling layer becomes good by setting the mass ratio of the acrylic component to the urethane component within the above range.

[0126] The primer layer preferably contains an antiblocking agent. Examples of antiblocking agents include inorganic particles and organic particles such as silica, alumina, aluminum hydroxide, barium sulfate, talc, and calcium carbonate. Among these, inorganic particles are preferred, and among the inorganic particles, silica is preferred.

[0127] The average particle diameter of the antiblocking agent is preferably about 0.1 to 10 μm, more preferably 0.5 to 8 μm, and even more preferably in the range of 0.5 to 5 μm. The particle diameter of the antiblocking agent is measured as the mass average value d50 in the measurement of particle size distribution by the laser light diffraction method. The content of the antiblocking agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

[0128] 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.

[0129] 〔Decoration layer〕 The transfer layer may have a decoration layer in order to enhance the design property. The decoration layer is preferably formed between the release layer and the adhesive layer.

[0130] The decoration layer may be formed on the entire surface of the transfer sheet or only on a part thereof.

[0131] Examples of the decoration layer include a colored layer formed by solidly coating ink; a pattern layer formed by printing ink as a pattern; a metal thin film; and the like. Examples of the pattern (design) expressed by the decoration layer include a wood grain pattern such as annual rings and conduit grooves on the surface of a wood board; a stone grain pattern on the surface of a stone slab such as marble and granite; a cloth grain pattern on the surface of a fabric; a leather grain pattern on the surface of leather; a tile pasting pattern including a joint groove; a brick stacking pattern including a joint groove; a matte pattern; a satin pattern; a pattern formed by arranging a plurality of concave and convex portions extending in parallel directions (so-called "ten thousand-line uneven pattern" or "ray engraving pattern"); an abstract pattern such as a geometric pattern, characters, figures, polka dots, and floral patterns; and the like.

[0132] As the ink used for the colored layer and the pattern layer, a mixture of a binder resin with a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. is appropriately used. There is no particular limitation on the binder resin of the colored layer and the pattern layer. For example, resins such as 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, and cellulose acetate resin can be mentioned. In addition, various types of resins such as one-component curing type resins and two-component curing type resins accompanied by a curing agent such as an isocyanate compound can be used.

[0133] There are no particular restrictions on the colorant, and the colorants exemplified in the adhesive layer can be preferably used. The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and still more preferably 30 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the resin constituting the decorative layer.

[0134] The colored layer and the pattern layer may contain additives such as an ultraviolet absorber, a light stabilizer, and a colorant. The thickness of the colored layer and the pattern layer may be appropriately selected according to the desired pattern. However, in order to improve the design property, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and still more preferably 2 μm or more and 5 μm or less. When it is necessary to conceal the color and appearance of the adherend, the thickness of the colored layer and the pattern layer is preferably 1.5 μm or more, although it depends on the type and content of the colorant contained.

[0135] Examples of the metal thin film include a thin film of a single metal element such as gold, silver, copper, tin, iron, nickel, chromium, cobalt, etc.; a thin film of an alloy containing two or more of the above metal elements; etc. Examples of the alloy include brass, bronze, stainless steel, etc. The film thickness of the metal thin film can be about 0.1 μm or more and 1 μm or less.

[0136] The above-described release layer, primer layer, adhesive layer, and decorative layer can be formed, for example, by applying a coating solution containing a composition for forming each layer onto a release support by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma coating method, etc., and drying and curing as necessary.

[0137] <Separator> The transfer sheet may have a separator on the side opposite to the release support of the transfer layer. 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 also makes it easier to prevent the transfer sheet from accidentally sticking to other objects.

[0138] The material of the separator is not particularly limited as long as it can be peeled off from the transfer layer, and a plastic film is preferably used. As the plastic film used as the separator, the same ones as those exemplified for the above-mentioned support can be used. It is preferable that the surface of the separator in contact with the transfer layer is subjected to a release treatment 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.

[0139] [[60° gloss value]] The transfer sheet of the present embodiment is capable of forming a transfer layer having excellent visibility of the matting effect on the adherend. In this specification, "matting" means that the gloss is difficult to visually recognize, and it cannot be generally stated because it varies depending on the color tone of the transfer layer. For example, if the 60° gloss value is 20.0 or less, preferably about 10.0 or less, it is generally treated as "matting". Further, since the transfer sheet of the present embodiment imparts matting, the above 60° gloss value means the 60° gloss value that the transfer sheet of the present embodiment can impart (the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend). If the transfer layer constituting the transfer sheet of the present embodiment has a stable matting effect and texture due to the formation of wrinkles, the decorative material obtained by transferring the transfer layer to the adherend can also be a high-quality decorative material having a stable visibility of the matting effect and texture. The 60° gloss value of the release support constituting the transfer sheet and the 60° gloss value of the decorative material obtained by transferring the transfer layer to the adherend are basically the same as long as their color tones are similar, although some differences may occur.

[0140] Up until now, for example, in the case of a decorative material that has a dark color such as black, it has been possible to impart excellent visibility of a matte effect with a 60° gloss value of 20.0 or less, preferably 10.0 or less, by adding a matte agent to the matte layer. A "dark color" is a color with low lightness, for example, a CIE (International Commission on Illumination) L value measured in accordance with JIS Z8781-4:2013. * a * b * L in color space * value (hereinafter simply referred to as "L * This is sometimes referred to as the "60° gloss value." This means that the 60° gloss value is usually about 40 or less, and preferably 30 or less. However, since a large amount of matting agent is used, streaks and unevenness occur during the formation of the matte layer, making it difficult to manufacture, and there is also the problem of reduced strength of the matte layer. In addition, 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. This tendency becomes more pronounced as the 60° gloss value is reduced. Therefore, in the conventional technology using a matting agent, it is necessary to reduce the amount of the matting agent used for manufacturing reasons, etc., and therefore it has not been possible to obtain a more excellent matting effect in terms of visibility.

[0141] 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 small as described above, so that not only is it possible to obtain a stable and extremely excellent matte effect visibility and texture, but also a rough touch. In addition, by limiting the amount of wrinkle formation stabilizer used to an extremely small amount, a significant increase in the viscosity of the resin composition can be suppressed, thereby improving the productivity of the matte layer.

[0142] The 60° gloss value of the decorative material obtained using the transfer sheet of the present embodiment varies depending on the color tone as described above and thus cannot be generally specified. However, for example, when presenting black or other dark colors, the 60° gloss value on the transfer layer side can be 10.0 or less, further 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, 2.0 or less, and can exhibit extremely excellent visibility of the matte effect. Also, decorative materials presenting color tones other than black or other dark colors can also have the above 60° gloss value. In this specification, the 60° gloss value on the transfer layer side refers to the 60° specular glossiness measured in accordance with JIS K 5600-4-7:1999, and is the average value of the values that can be measured from the transfer layer side using a gloss meter or the like at any 10 locations. When measuring the 60° gloss value, in order to suppress the reflection on the back surface of the sample, it is preferable to bond a black plate to the back surface of the measurement sample via an adhesive layer.

[0143] [Method for manufacturing a decorative material] The method for manufacturing the decorative material of the present embodiment has the following steps (1) and (2). (1) A step of obtaining a laminate in which the transfer layer side of the transfer sheet of the present embodiment described above is in close contact with an adherend. (2) A step of peeling the release support from the laminate to obtain a decorative material having a transfer layer on the adherend.

[0144] The adherend in step (1) is not particularly limited, and an adherend made of a resin, paper, non-woven fabric, woven fabric, wood, metal, non-metallic inorganic material, etc. can be appropriately selected. When using a resin as the adherend, in order to improve the adhesion between the transfer layer of the transfer sheet and the adherend, if desired, physical or chemical surface treatments such as an oxidation method and a roughening method can be performed on one or both sides. The shape of the adherend is not particularly limited, and it may be a flat plate shape such as a sheet shape, or may have a three-dimensional shape such as a curved plate or a polygonal prism.

[0145] In step (1), the transfer layer side of the transfer sheet and the adherend can be adhered to each other, for example, by the adhesive layer of the transfer layer. When the transfer layer does not have an adhesive layer, in step (1), an adhesive may be interposed between the transfer layer and the adherend.

[0146] As one embodiment of step (1), a method by a laminating method having the following steps (a1) and (a2) in order can be mentioned. (a1) A step of bringing the surface on the transfer layer side of the transfer sheet into contact with and overlapping the adherend on the flat plate. (a2) A step of heating and / or applying pressure from the release support side of the transfer sheet to adhere the adherend on the flat plate and the transfer layer of the transfer sheet.

[0147] Also, as another embodiment of step (1), a method by in-mold molding that requires the following steps (z1) to (z4) in order can be mentioned. In in-mold molding, the resin poured in step z2 becomes the adherend. (z1) A step of arranging the transfer layer side of the transfer sheet facing the inside of the in-mold molding die. (z2) A step of injecting and injecting resin into the in-mold molding die. (z3) A step of integrating the transfer sheet and the resin to adhere the transfer layer of the transfer sheet and the resin to form a resin molded body. (z4) A step of taking out the resin molded body from the in-mold molding die.

[0148] When the transfer sheet has a separator on the side opposite to the release support of the transfer layer, it is preferable to have the following step (0) before the step (1). (0) A step of peeling the separator from the transfer sheet.

[0149] The decorative material obtained as described above can be arbitrarily cut, and arbitrary decorations such as grooving and chamfering can be applied to the surface and the end face using a cutting machine such as a router or a cutter. And it can be suitably used for various applications, for example, interior members of buildings such as walls, ceilings, and floors, exterior members such as exterior walls, eaves, roofs, fences, and fences, building fixtures or architectural members such as window frames, doors, door frames, handrails, baseboards, moldings, and trims, as well as general furniture such as wardrobes, shelves, and desks, kitchen furniture such as dining tables and sinks, various furniture and members used in wet areas such as kitchens, toilets, bathrooms, and washbasins, or surface decorative panels such as cabinets for home appliances and OA equipment, interior or exterior members of vehicles, various members such as signboards and soundproof walls. That is, the transfer sheet of the present embodiment is suitably used as a transfer sheet for transferring the concavo-convex shape to these various members. Furthermore, in addition to the above-mentioned various members, the decorative material can be used alone or in a laminated or composite form with other materials for packaging materials, anti-glare films for displays, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, transparent plates such as windows, doors, and partitions (window glass, show windows, etc.), artificial leather, etc.

[0150] [Decorative material] The decorative material of the present embodiment is a decorative material having a transfer layer on a adherend, and at least a part of the surface of the transfer layer on the side opposite to the adherend has a surface shape defined in ISO25178-2:2012, where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50.

[0151] FIG. 6 is a cross-sectional view showing an embodiment of the decorative material 200 of the present invention. The decorative material 200 in FIG. 6 has a transfer layer 20 on an adherend 30. Further, in FIG. 6, the transfer layer 20 has an adhesive layer 24, a decorative layer 23, a primer layer 22, and a release layer 21 in this order from the side closer to the adherend 30. 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 surface shape in which Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50.

[0152] Examples of the adherend constituting the decorative material of the present embodiment include the adherends exemplified in the manufacturing method of the decorative material of the present embodiment. Examples of the transfer layer constituting the decorative material of the present embodiment include the transfer layers exemplified in the transfer sheet of the present embodiment.

Examples

[0153] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

[0154] 1. Evaluation 1-1. Measurement of surface shape Regarding the surface shape on the release layer side of the decorative materials obtained in the examples and comparative examples, Ssk (skewness), Sku (kurtosis), Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) were measured. The measurement area was a rectangular (1024 μm × 768 μm) area at an arbitrary location on the surface of the decorative material. The measuring device used was a shape analysis laser microscope (「VK-X150 (control unit) / VK-X160 (measurement unit)」, manufactured by KEYENCE CORPORATION), with an objective lens: 50 times, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, and measurement quality: high-speed mode. Also, the cut-off values of Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) were set to 0.8 mm. The surface shape on the release layer side of the decorative material can be regarded as the surface shape on the mold release support side of the transfer layer.

[0155] 1-2. 60° gloss value Samples were prepared by bonding a black plate to the back surface of the polycarbonate resin sheet of the cosmetic materials obtained in the examples and comparative examples via an adhesive layer. From the release layer side of the samples, the 60° specular glossiness was measured in accordance with K 5600-4-7:1999 using a gloss meter (“Micro Gloss (model name)”, manufactured by BYK Gardner).

[0156] 1-3. Evaluation of texture before the weather resistance test Regarding the cosmetic materials obtained in the examples and comparative examples, 20 arbitrary adults were asked to evaluate the surface texture (uniformity of the surface state), and the evaluation was conducted according to the following criteria. A: 18 or more people evaluated that the surface state was uniform and the visibility of the matting effect was high. B: 15 to 17 people evaluated that the surface state was uniform and the visibility of the matting effect was high. C: 14 or fewer people evaluated that the surface state was uniform and the visibility of the matting effect was high.

[0157] 1-4. Evaluation of texture after the weather resistance test Regarding the cosmetic materials obtained in the examples and comparative examples, the following weather resistance test was conducted. Regarding the cosmetic materials after the weather resistance test, the surface texture (uniformity of the surface state) was evaluated according to the same criteria as in 1-3. <Weather resistance test> The weather resistance test was conducted using a weather resistance test device (trade name “Metal Weather” manufactured by Dipla·Wintes Co., Ltd.). In the weather resistance test, the following “ultraviolet irradiation process”, “dew condensation process”, and “water spray process” were defined as one cycle, and the cycle was repeatedly performed until 500 hours had elapsed. 《Ultraviolet irradiation process》 Illuminance: 60 mW / cm 2 , black panel temperature: 63 °C, humidity inside the tank: 50% RH, time: 20 hours 《Dew condensation process》 Illuminance: 0 mW / cm 2 , black panel temperature: 30 °C, humidity inside the tank: 98% RH, time: 4 hours 《Water spray process》 Water is sprayed for 10 seconds before and after the dew condensation process.

[0158] Evaluation of a rough touch from 1 to 5 Regarding the cosmetic materials obtained in the examples and comparative examples, as the standard for the rough touch, Oxford fabric using 40-count cotton yarn was used, and 20 arbitrary adults were asked to evaluate the surface touch and evaluated according to the following criteria. A: 18 or more people evaluated that the touch was close to the standard and was a rough touch. B: 15 to 17 people evaluated that the touch was close to the standard and was a rough touch. C: 14 or fewer people evaluated that the touch was close to the standard and was a rough touch.

[0159] 2. Preparation of the matting layer [Matting layer 1] A resin composition containing an acrylic resin and a urethane resin as binder resins was applied to one surface of a substrate (a corona-discharge-treated polypropylene sheet, thickness: 100 μm), and dried to form an easy-adhesion layer (thickness: 2 μm). On the easy-adhesion layer, the following resin composition 1 for forming a matting layer was applied by the gravure method (coating amount: 5 g / m 2 (when dry)), then irradiated with ultraviolet rays using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet ray amount: 6 W / cm 2 ), then irradiated with ultraviolet rays using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet ray output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm 2 , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and then further irradiated with ultraviolet rays using a high-pressure mercury lamp (ultraviolet ray output density: 200 W / cm) to obtain a laminate 1 having a matting layer 1 on the substrate.

[0160] [Resin composition 1 for forming a matting layer] · Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Bifunctional acrylate monomer: 35 parts by mass · Wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass · Anti-wrinkle stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass · Photoinitiator (benzophenone type): 0.8 parts by mass

[0161] [Matte layer 2] A laminate 2 having a matte layer 2 on a substrate was obtained in the same manner as matte layer 1, except that the resin composition 1 for forming a matte layer was changed to the following resin composition 2 for forming a matte layer.

[0162] [Resin composition 2 for forming a matte layer] · Bifunctional acrylate monomer: 100 parts by mass · Anti-wrinkle stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass · Anti-wrinkle stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass · Photoinitiator (benzophenone type): 0.8 parts by mass

[0163] [Matte layer 3] A laminate 3 having a matte layer 3 on a substrate was obtained in the same manner as matte layer 1, except that the resin composition 1 for forming a matte layer was changed to the following resin composition 3 for forming a matte layer and only irradiated with an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3 Mrad)).

[0164] [Resin composition 3 for forming a matte layer] · Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Bifunctional acrylate monomer: 35 parts by mass · Matting agent (average particle diameter: 8.0 μm): 15.0 parts by mass · Photoinitiator (benzophenone type): 0.8 parts by mass

[0165] 3. Preparation of a release support, a transfer sheet, and a decorative material [Example 1] A resin composition containing an acrylic resin and a urethane resin as binder resins was applied to one surface of a support (a corona-discharge-treated PET sheet, thickness: 100 μm) and dried to form an easy-adhesion layer (thickness: 2 μm). Next, the following resin composition for forming a release layer was applied onto the easy-adhesion layer by the gravure method to form a coating film (coating amount: 5 g / m 2 (when dried)), and a laminate 1' having an easy-adhesion layer and an uncured release layer was obtained on the support. Next, the surface of the matting layer 1 side of the above laminate 1 was dry-laminated onto the uncured coating film (uncured release layer) of the laminate 1' to obtain a laminate 1". Next, the laminate 1" was irradiated with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) from the PET side of the laminate 1' constituting the laminate 1" to cure the uncured release layer. Next, the laminate 1 was peeled off from the laminate 1", and a release support used in Example 1 having an easy-adhesion layer and a release layer was obtained on the support. On the release layer of the release support used in Example 1, a shape in which the surface shape of the matting layer 1 was inverted was formed.

[0166] Next, the following resin composition 1 for forming a peeling layer was applied onto the release layer of the release support to form an uncured resin layer, and the uncured resin layer was cured by irradiation with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to form a peeling layer (thickness: 5 μm). Thereafter, corona irradiation was performed on the peeling layer. Next, the following resin composition for forming a primer layer was applied and dried onto the corona-irradiated peeling layer 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 and dried onto the above primer layer to form an adhesive layer having a heat-sealing property with a thickness of 4 μm. After forming the adhesive layer, aging was performed at room temperature for 24 hours to obtain the transfer sheet of Example 1.

[0167] The adhesive layer of the transfer sheet of Example 1 was opposed to and laminated with one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC, trade name "Carbo Polish") as the adherend. Thereafter, from the transfer sheet side, using a laminator (roll-type thermal transfer machine manufactured by Navitas, product number "RT-300"), pressure was applied while heating under the conditions of a laminating 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 was in close contact with the adherend. 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.

[0168] <Resin composition for forming release layer> · 100 parts by mass of urethane acrylate oligomer · 0.5 part by mass of reactive acrylic-modified silicone oil

[0169] <Resin composition 1 for forming release layer> · Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 100 parts by mass · Ultraviolet absorber (BASF, trade name: Tinuvin479): 0.5 part by mass · Light stabilizer (BASF, trade name: Tinuvin123): 0.3 part by mass

[0170] <Resin composition for forming primer layer> · Polycarbonate-based urethane acrylate copolymer: 100 parts by mass (Weight average molecular weight 50,000) · Ultraviolet absorber (BASF, trade name: Tinuvin479): 20 parts by mass · Ultraviolet absorber (BASF, trade name: Tinuvin400): 15 parts by mass · Light stabilizer (BASF, trade name: Tinuvin123): 3.5 parts by mass · Anti-blocking agent (silica with an average particle diameter of 3 μm): 10 parts by mass · Solvent: appropriate amount

[0171] [Example 2] Except that laminate 1 was changed to laminate 2 when obtaining the releasable support, in the same manner as in Example 1, the releasable support, transfer sheet and decorative material of Example 2 were obtained. On the release layer of the releasable support used in Example 2, a shape obtained by inverting the surface shape of the matting layer 2 was shaped.

[0172] [Example 3] A releasable support, a transfer sheet, and a decorative material of Example 3 were obtained in the same manner as in Example 1, except that the resin composition 1 for forming a release layer was changed to the following resin composition 2 for forming a release layer. On the release layer of the releasable support used in Example 3, a shape obtained by inverting the surface shape of the matting layer 1 is formed.

[0173] <Resin composition 2 for forming a release layer> · Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 40 parts by mass · Ionizing radiation curable resin (hexafunctional urethane acrylate oligomer): 60 parts by mass · Ultraviolet absorber (BASF, trade name: Tinuvin 479): 2 parts by mass · Light stabilizer (Nippon Emulsion Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[0174] [Comparative Example 1] A releasable support, a transfer sheet, and a decorative material of Comparative Example 1 were obtained in the same manner as in Example 1, except that the laminate 1 when obtaining the releasable support was changed to the laminate 3. On the release layer of the releasable support used in Comparative Example 1, a shape obtained by inverting the surface shape of the matting layer 3 is formed.

[0175]

Table 1

[0176] From the results in Table 1, it was confirmed that the decorative material obtained using the transfer sheet of the present embodiment has a 60° gloss value of 1.6 on the release layer side of the decorative material, is extremely excellent in the visibility of the matting effect, and is also excellent in texture. It was also confirmed that it was excellent in the rough touch. On the other hand, in the transfer sheet of Comparative Example 1, even when a large amount of matting agent was contained in the reference matting layer, no wrinkles were formed on the surface of the matting layer, so no wrinkles were formed on the surface of the transfer layer either. Therefore, it was confirmed that the 60° gloss value of the decorative material obtained using the transfer sheet of Comparative Example 1 was 8.3, inferior to the gloss value of the transfer sheet of the example, and inferior in texture.

[0177] Figure 7 is an optical microscope image of the release layer side of the cosmetic material obtained using the transfer sheets of Example 1 and Example 3, and Figure 8 is an optical microscope image of the release layer side of the cosmetic material obtained using the transfer sheet of Example 2 (in both cases, the horizontal width of the image corresponds to 272.0 μm). According to the optical microscope images (Figures 7 to 8 respectively) of Examples 1 to 3, it can be confirmed that the cosmetic materials of these examples have irregular wrinkles on their surfaces. On the other hand, according to the optical microscope image of Comparative Example 1 (Figure 9), wrinkles like those of the cosmetic materials of the examples were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed, and the surface state was unstable (not uniform), and it could not be said to be excellent in texture. From this result, it was confirmed that the transfer sheet of the present embodiment exhibits a specific surface shape due to the wrinkles on its surface, and due to that surface shape, it has extremely excellent visibility of the matting effect and texture, and is excellent in a rough touch feeling.

Explanation of symbols

[0178] 100: Transfer sheet 200: Cosmetic material 10: Release support 11: Support 12: Release layer 20: Transfer layer 21: Release layer 22: Primer layer 23: Decorative layer 24: Adhesive layer 30: Adherend 2: Recess 3: Convex part (protrusion)

Claims

1. A transfer sheet having a transfer layer on a release support, at least a part of the surface of the transfer layer on the release support side has a surface shape defined in ISO 25178-2:2012, where Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50, and the 60° gloss value imparted by the part of the transfer layer having the surface shape is 10.0 or less.

2. The transfer sheet according to claim 1, wherein Rsm (average length of curve elements), which is a lateral parameter of the contour curve defined in JIS B0601:2013 of the surface shape, is 100.00 μm or less.

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

4. The transfer sheet according to any one of claims 1 to 3, wherein Ra (arithmetic mean roughness), which is a height direction parameter of the contour curve defined in JIS B0601:2013 of the surface shape, is 5.50 μm or less.

5. The transfer sheet according to any one of claims 1 to 4, wherein the surface of the transfer layer forming the surface shape has an uneven shape composed of irregular wrinkles.

6. The transfer sheet according to claim 5, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and concave portions formed by being surrounded by the plurality of linear protrusions.

7. The transfer sheet according to any one of claims 1 to 6, wherein the transfer layer has a release layer and an adhesive layer in this order from the release support side.

8. The transfer sheet according to claim 7, having one or more layers selected from a primer layer and a decorative layer between the release layer and the adhesive layer.

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

10. The transfer sheet according to any one of claims 7 to 9, wherein the release layer contains an ultraviolet absorber or a light stabilizer.

11. The transfer sheet according to any one of claims 7 to 10, wherein the release layer substantially does not contain particles.

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

13. The transfer sheet according to claim 12, wherein the release layer contains a cured product of a resin composition containing a radiation curable resin.

14. A method for manufacturing 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 13 is in close contact with an adherend. (2) A step of peeling the releasable support from the laminate to obtain a decorative material having a transfer layer on the adherend.

15. A decorative material having a transfer layer on an adherend, having a surface shape defined in ISO 25178-2:2012 on at least a part of the surface of the transfer layer on the side opposite to the adherend, wherein Ssk (skewness) is 0.00 or more and Sku (kurtosis) is more than 3.50, and the 60° gloss value of the portion having the surface shape is 10.0 or less.

Images