Transfer sheet, method for manufacturing 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 moist touch feeling.SOLUTION: A transfer sheet has a transfer layer on a releasable support, and has a surface shape of Ssk (skewness) of less than 0.00 which is 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 panels for cabinets of home appliances, OA equipment, etc., 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 decorative materials used for these applications, a technique of improving the texture by using a matting effect (mat effect) to improve the design property is widely used. As a decorative material using a matting 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 enhancing the pattern layer and the concealing layer is obtained. In its example, a mat ink in which 50 parts by weight in total of spherical alumina 10 parts by weight and calcium carbonate 40 parts by weight is added 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 a method of 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 damages the coating film, 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 further, the matting agent itself adsorbs contaminants, 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 matte effect using a matting agent. In addition, when using embossing as in Patent Document 2, the production of the embossing plate is very 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-described visual dulling effect but also tactile expression is increasingly demanded. For example, when using a dulling agent as in Patent Document 1 above, by increasing the amount of its use, the outline of the dulling agent appears on the surface of the decorative sheet, and a somewhat rough tactile sensation may be expressed. Also, when using embossing as in Patent Document 2, a tactile sensation may be expressed due to the uneven shape of the surface formed by the embossing die. However, in either case, the focus is not on the expression of the tactile sensation, and the situation is that sufficient expression cannot be said in terms of the tactile sensation. That is, the conventional decorative sheet could not achieve both an excellent dulling effect and a tactile sensation. In the present invention, particular attention was paid to a "moist" tactile sensation among the tactile sensations. Furthermore, as an embodiment of imparting design properties to the surface of an article such as a decorative sheet, both a decorative layer such as an uneven shape and a pattern layer are often 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 a problem that the process time becomes long and the manufacturing cost also becomes high.

[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 moist tactile sensation, and 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, The transfer sheet having a surface shape defined in ISO 25178-2:2012 with Ssk (skewness) less than 0.00 on at least a part of the surface of the transfer layer on the release support side. [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] and the adherend are in close contact. (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 the adherend, A decorative material having a surface shape defined in ISO25178-2:2012 with Ssk (skewness) less than 0.00 on at least a part of the surface on the side opposite to the adherend of the transfer layer.

Advantages of the Invention

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

Brief Description of the Drawings

[0011]

Figure 1

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Best Mode 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 "or more", "or less" and "~" in 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 for 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 in which Ssk (skewness) defined in ISO25178-2:2012 is less than 0.00.

[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 in which Ssk (skewness) is less than 0.00.

[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) less than 0.00 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 matting effect (hereinafter, these may be collectively referred to as the "matting effect") to the adherend, and as a tactile sensation, especially a "moist" tactile sensation can be imparted to the adherend. The "moist" tactile sensation is a sensory expression, but in this specification, "moist" includes all tactile sensations that are generally felt as "moist". Specifically, it means the tactile sensation felt when touching a smooth, moist surface with the pad of a finger. Examples of those having a "moist" tactile sensation include natural fiber fabrics such as silk and tencel, synthetic fibers such as promix, rayon, and cupra, chemical fiber fabrics such as recycled fibers, or fabrics obtained by peach skin processing (a thin napping process having a tactile sensation similar to the skin of a peach fruit) of these chemical fiber fabrics.

[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 mean plane. When Ssk is 0, the surface shape is symmetric (normal distribution) with respect to the mean plane. When Ssk exceeds 0, it can be understood that the surface shape is biased downward, i.e., the lower height side, with respect to the mean plane, 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, i.e., the higher height side, with respect to the mean plane (the horizontal line in FIGS. 1 and 2), 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) is less than 0 (1-1) and the case where it exceeds 0 (1-2). The fact that Ssk (Skewness) of the surface shape in the present embodiment is less than 0.00 indicates that it tends to have the shape shown in (1-1). That is, since the surface shape is biased upward with respect to the mean plane (the horizontal line in FIG. 1), above the mean plane, i.e., as the surface shape imparted by the transfer sheet of the present embodiment, there are many convex parts with a wide width with respect to the height (low aspect ratio) and a cross-sectional shape close to a rectangle (trapezoid), and it can be said that the convex parts are distributed closely. Since the surface shape has such a shape, when touched with the fingertip, the contact area is large, so a catching feeling is felt, which is considered to lead to the tactile sensation felt when touching a smooth and moist surface. Further, since such convex parts exist, there are relatively concave parts between the convex parts, so it is considered that a matting effect is also obtained. Details of the manifestation of the matting effect will be described later. From the viewpoint of improving the matting effect and the moist touch feeling, Ssk (Skewness) is preferably -0.10 or less, more preferably -0.25 or less, still more preferably -0.45 or less, and preferably -3.00 or more as the lower limit, preferably -2.00 or more, more preferably -1.50 or more, and even more preferably -1.30 or more.

[0017] The measurement of Ssk (skewness) is a measured value obtained 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 to the adherend. The measurement conditions can be adjusted as appropriate. For example, it is possible to measure 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] In the present embodiment, as the surface shape, it is preferable that Sku (kurtosis) defined in ISO 25178-2:2012 is 3.00 or more. Sku (kurtoisis) 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 average plane. When Sku is 3, the surface shape is symmetric (normal distribution) with respect to the average 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 have a flattened shape. The tendency of the shape exhibited by the surface shape indicated by Sku (kurtoisis) will be described with reference to FIG. 2. FIG. 2 is a schematic diagram when Sku (kurtoisis) exceeds 3.000 (2-1) and when it is less than 3.00 (2-2). The fact that Sku (kurtoisis) of the surface shape in the present embodiment is 3.00 or more means that it has the shape shown in (2-1), has the most height portions around the average height, and has a height distribution such that both the portion where the height is greatly protruding above the average height and the portion where the height is greatly decreasing below the average height are small. It can be said that the tip shape of the convex portion existing above the average plane has a sharp shape but the number is small. In the surface shape satisfying the above Ssk (skewness), when Sku (kurtoisis) is 3.00 or more, on the region of the convex portion having a wide width and a low aspect ratio shape with respect to the height, there are a small number of protruding portions at the tip shape and concave portions (acute angles) where the bottom is recessed scattered. Therefore, when touched with the pulp of the finger, the contact area does not spread widely over the entire surface like a simple flat surface (mirror surface), but is appropriately divided by the scattered protruding portions and concave portions and becomes small, so that the catching feeling of the pulp of the finger is within an appropriate range and the moist touch feeling is improved. Also, the dulling effect is improved.

[0019] From the viewpoint of improving the dulling effect and the moist touch feeling, Sku (kurtoisis) is preferably 3.05 or more, more preferably 3.10 or more, still more preferably 3.15 or more, and the upper limit is preferably 5.50 or less, more preferably 5.25 or less, still more preferably 5.00 or less.

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

[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 smaller the value of Rsm (average length of curve elements), the narrower the width of the convex portion, and it becomes an index indicating that the surface shape tends to have narrower convex portions. Therefore, in the surface shape that satisfies the above Ssk (skewness), 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 contact area when touched with the fingertip becomes smaller, so that the snagging condition becomes appropriate and the moist touch feeling is improved. Also, the dulling effect is improved. From the viewpoint of improving the dulling effect and the moist touch feeling, Rsm (average length of curve elements) is preferably 90.00 μm or less, more preferably 80.00 μm or less, still more preferably 65.00 μm or less, and even more preferably 55.00 μm or less, and as the lower limit, it is preferably 20.00 μm or more, more preferably 25.00 μm or more, still more preferably 30.00 μm or more. In addition, when measuring 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 3.00 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 portion is in shape as seen from the valley, and it becomes an index indicating that there tends to be many such convex portions. Therefore, in the surface shape satisfying the above Ssk (skewness), when Rz (maximum height) is 3.00 μm or more, the resistance feeling due to each large (high) convex portion as seen from the valley when touched with the fingertip increases, so that the moist touch feeling is improved. Also, the matting effect is improved. From the viewpoints of improving the matting effect and the moist touch feeling, Rz (maximum height) is preferably 3.50 μm or more, more preferably 4.00 μm or more, still more preferably 4.50 μm or more, even more preferably 4.80 μm or more, and as the upper limit, it is preferably 15.00 μm or less, more preferably 13.50 μm or less, still more preferably 11.00 μm or less, even more preferably 10.00 or less. In the measurement of 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 2.00 μm or less. Ra (Arithmetic Mean Roughness) is one of the parameters in the height direction of the contour curve and is the average value of the height difference 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 and the corresponding concave portions in the surface shape tend to be, indicating an index that the surface shape tends to be smoother and more uniform. Therefore, in the surface shape that satisfies the above Ssk (Skewness), when Ra (Arithmetic Mean Roughness) is 2.00 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 feeling is suppressed, and in particular, the moist touch feeling is improved. Also, the dulling effect is improved. From the viewpoint of improving the dulling effect and the moist touch feeling, Ra (Arithmetic Mean Roughness) is preferably 1.95 μm or less, more preferably 1.90 μm or less, still more preferably 1.80 μm or less, and preferably 0.10 μm or more, more preferably 0.40 μm or more, still more preferably 0.60 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 layer that stably exhibits a dulling effect due to the light diffusion effect caused by the shape of the wrinkles and also exhibits a moist touch feeling 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 appearing on at least one surface of the transfer layer have a surface shape having Ssk (skewness) within the above specific numerical range (preferably, further having a surface shape having Sku (kurtosis), Rsm (average length of curve elements), Rz (maximum height), Ra (arithmetic mean roughness) within the above specific numerical range), and there is no particular limitation as long as it exhibits such a surface shape. Thus, since the appearance of wrinkles makes it easier to satisfy the above surface shape, the appearance of wrinkles enables the stable expression of a matting effect and also the expression of a moist touch feeling. Regarding the wrinkles, from the viewpoint of expressing the above surface shape, improving the matting effect, and improving the moist touch feeling, 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, and 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 will be described later. In the present embodiment, more preferable 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.

[0026] Examples of the aspects regarding these wrinkles include the aspect shown in FIG. 5. In FIG. 5, the surface of the transfer layer has irregular wrinkles in a plan view, and the irregular wrinkles are composed of including 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). Also shown is that 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 the present embodiment stably exhibits a matting effect and also a moist touch feeling due to the wrinkles shown in FIG. 5.

[0027] Here, "curved" means having at least one portion in a plan view where the extending direction of the convex portion 3 of the continuous strip reverses from one side to the other side. 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 strip 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 strip is ignored, a form having a V-shaped broken line or a portion approximated by two sides sandwiching one vertex of a triangle, etc. can be mentioned. Also, "meandering" means having at least two or more portions in a plan view where the extending direction of the convex portion 3 of the continuous strip reverses from one side to the other side (hereinafter, also referred to as "reversing portion"), and when advancing the convex portion 3 of the strip in its extending direction, having a portion where the extending direction of the convex portion 3 of the strip 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 strip is ignored, a form having a portion approximated by the Roman letter "S" can be mentioned. Also, when approximated by a straight line when the width of the planar shape of the convex portion 3 of the strip is ignored, a form having a portion approximated by the Roman letter "W" can be mentioned.

[0028] In this specification, "irregular" means not having a shape with a certain law or being so-called patterned and arranged with a certain law. Typical examples of a non-irregular shape (regular shape) 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 one protrusion itself is irregular and not formed with a certain law such as periodicity, that the shapes of the plurality of convex portions formed by the plurality of protrusions are not formed and arranged with a certain law, and that 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 of each of a plurality of protrusions (a plurality of convex portions), and their arrangement, and the shape of the recess surrounded by the plurality of protrusions is irregular, a dulling effect due to having irregular wrinkles and a moist 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 moist 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 is the convex portion, and the region with a height equal to or less than the median value is 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 as gradation 255, and the lightest portion in the density distribution image is set as 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 moist 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 irregularity but a certain degree of uniformity, 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-described surface shape, and is not a preferable aspect in terms of the visibility and texture of the matting effect, nor is it a preferable aspect in terms of obtaining a moist 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 matting effect and improving the moist touch will be described below. When the wrinkles have the following shapes, it becomes easier to exhibit the above-described surface shape, and the matting effect and the moist 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-described surface shape, and in relation to the concave portion, the matting effect is stably improved and the moist 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 portions, the matting effect is stably improved, and a moist touch is improved. Here, the dimensions of the recess are determined in the same manner as the dimensions of the convex portions 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 a moist touch is improved. Here, the dimensions of the recess are determined in the same manner as the dimensions of the convex portions described above.

[0034] The occupancy ratio of the convex portions 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 portions is within the above range, it becomes easier to exhibit the above surface shape, and in relation to the occupancy ratio of the recesses surrounded by the convex portions, the matting effect is stably improved, and a moist touch is improved. Here, the occupancy ratio of the convex portions is the average value of the occupancy ratios of the convex portions in any 10 locations (10 regions of 100 μm square) 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 moist touch feeling, it is preferable that their length is short. Specifically, the length in which the convex and concave portions with 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 moist touch feeling 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 that they are generally the same, and in the case of direction, it means a difference within ±3°, and in the case of width, it means a difference within ±5%.

[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 moist touch feeling 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 may be used. 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 "same" here 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 produce a basic matte layer, and then use, as the surface shape of the release support, the 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), and (3-1) to (3-2).

[0040] Produce a basic dulling layer 1 that satisfies parameters such as Ssk. (1-2) Press the dulling layer 1 against the surface of the mold-releasing support, and impart a shape that is the reverse of the surface shape of the dulling layer 1 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 pressing the dulling layer 1 against the surface of the mold-releasing layer, if the mold-releasing 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 mold-releasing layer (= the surface of the mold-releasing support).

[0041] Produce a basic dulling layer 1 that satisfies parameters such as Ssk. (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 mold-releasing 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 mold-releasing support. As the mold-releasing support, a laminate having a mold-releasing layer on a support is used. When pressing the mold 1 against the surface of the mold-releasing layer, if the mold-releasing 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 mold-releasing layer (= the surface of the mold-releasing support).

[0042] (3-1) Design a surface shape that satisfies parameters such as Ssk by simulation, and produce a mold 3 that reproduces the designed surface shape by laser micromachining. (3-2) Press the mold 3 against the surface of the mold-releasing support, and impart a shape obtained by inverting the surface shape of the mold 3 (= a surface shape satisfying parameters such as Ssk) to the surface of the mold-releasing support. When using a laminate having a mold-releasing layer on a support as the mold-releasing support, if the mold-releasing layer is in an uncured state when pressing the mold 3 against the surface of the mold-releasing layer, 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 inverted once. Therefore, the mold-releasing support of this embodiment can also be manufactured by the following steps (4-1) to (4-3). (4-1) Produce a matte layer 2 having a surface shape obtained by inverting a surface shape satisfying parameters such as Ssk. (4-2) Produce a mold 4 having a surface shape obtained by inverting the surface shape of the matte layer 2. 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) Press the mold 4 against the surface of the mold-releasing support, and impart 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) to the surface of the mold-releasing support. When using a laminate having a mold-releasing layer on a support as the mold-releasing support, if the mold-releasing layer is in an uncured state when pressing the mold 4 against the surface of the mold-releasing layer, 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 mold-releasing layer surface 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) With respect to 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 a minute wrinkle structure 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 the 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 basic matting layer is (1) preferably forming a minute wrinkle structure on the surface of the matting layer. Furthermore, it is preferable that the basic matting layer (2) optimizes the composition and 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) optimizes the irradiation conditions of the resin composition for forming the matting layer, particularly the wavelength, integrated light amount, 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 substrate for forming the matting layer, the thickness of the matting layer, etc. By optimizing these, regarding the surface shape of the basic matting layer (= the surface shape of the transfer layer in the present embodiment), Ssk (skewness), etc. can be within the above specific numerical ranges, and preferably, Sku (kurtosis), Rsm (average length of curve elements), Rz (maximum height), and Ra (arithmetic mean roughness) can be easily within the predetermined numerical ranges.

[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 moist touch feeling, a base material composed of a resin and a base material composed of a fibrous material are preferable, and a base material composed of a resin is more preferable. Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable, olefin resins, vinyl chloride resins, and polyester resins are more preferable, polyethylene and polypropylene are preferable as olefin resins, polyvinyl chloride is preferable as vinyl chloride resins, and polyethylene terephthalate is preferable as polyester resins. Among the resins used for the base material, polyester resins are preferable, and polyethylene terephthalate is particularly preferable. Also, 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 moist touch feeling 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 above resin composition for forming the dulling layer, from the viewpoint of obtaining a dulling layer having an excellent dulling effect and an excellent moist touch feeling, a resin composition containing a resin and a wrinkle formation stabilizer (hereinafter, may be referred to as a "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 stabilizes the formation of wrinkles on at least one surface of the dulling layer, so that the visibility of the dulling effect is uniformly exhibited over the entire surface of the dulling layer, and partial unevenness of gloss is reduced. It 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) and a planar uniformity (also referred to as "texture"). And the wrinkles formed on the dulling layer also greatly contribute to the expression of a moist touch feeling. 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 substances and average particle diameters, their matting mechanisms (functions), structures for expressing matting, and relationships between the usage amount and the degree of surface gloss (gloss value) are different. Also, in terms of expressing a moist touch by forming wrinkles, it is different from the "matting agent".

[0050] In the prior art such as Patent Document 1, etc., the matting agent used for matting expression exhibits the visibility of the matting effect due to the light diffusion effect caused by its 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 and refraction at the refractive interface corresponding to the contour shape of the particles. 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, thereby stably imparting 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 substances and average particle diameters are the same), in terms of their matting mechanisms (functions), 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 it is contained in a specific amount C 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. G60° 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% of the thickness of the matting layer and more than 30 μm, from the viewpoint of forming convex portions by the protruding effect as described above, that is, the layer in which the matting agent can be contained, i.e., the matting layer.

[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 of the thickness of the matting layer and 30 μm or less. From the viewpoint of improving the matting effect and the smooth touch, it is preferable to use at least one of two kinds of wrinkle-forming stabilizers distinguished by their average particle diameters, 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 kinds of wrinkle-forming stabilizers are a wrinkle-forming stabilizer 1 with an average particle diameter 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 diameter of less than 1 μm. In this embodiment, if at least one of the two kinds of wrinkle-forming stabilizers is used, the formation of wrinkles is stable, a stable and excellent matting effect can be obtained, and a smooth 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 viewpoint of improving the matting effect and the smooth 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, fluorine-based resin, and polyester-based 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 diameter of the wrinkle-forming stabilizer 1 is 1 μm or more, and is capped at the smaller value of either 100% or less of the thickness of the matting layer and 30 μm or less. From the perspective of stably improving the matting effect and improving the smooth touch, the average particle diameter of the wrinkle-forming 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. The smaller value of any combination of the upper limit with respect to the thickness of the matting layer and the upper limit of the absolute value may be used. For example, the upper limit may be the smaller value of either 90% or less of the thickness of the matting layer and 20 μm or less, or the smaller value of either 90% or less of the thickness of the matting layer and 10 μm or less. The thickness of the matting layer will be described later.

[0056] In addition, the average particle diameter of the wrinkle-forming stabilizer 2 is less than 1 μm. From the perspective of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the smooth touch, the average particle diameter of the wrinkle-forming 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 diameter of the wrinkle-forming stabilizer is measured as the mass average value d50 in the particle size distribution measurement by the laser light diffraction method.

[0057] From the perspective of stabilizing the formation of wrinkles by a wrinkle-forming stabilizer, steadily improving the matting effect, and improving the moist touch, the content of the wrinkle-forming stabilizer (when using a combination of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2, it is the total content of these) 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, per 100 parts by mass of the resin forming the matting layer. As the upper limit, there is no particular limitation from the perspective of steadily improving the matting effect and improving the moist touch. However, for example, from the perspective 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 using a combination of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2, there is no particular limitation on the content of each of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 as long as the total content is within the above range. However, the content of 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, per 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. Also, the blending ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2, as the blending amount of wrinkle-forming stabilizer 1 when the total amount of these is 100 parts by mass, 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.

[0059] As the wrinkle-forming stabilizer, as described above, organic particles and inorganic particles can be used. 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, including 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, an extremely excellent matting effect is obtained compared to the effect obtained by the matting agent, and a moist touch is also obtained. Therefore, it can be said that the matting layer of the present embodiment, although substantially free of a matting agent, forms wrinkles stably on the surface, so that the visibility of a more excellent matting effect is stably obtained compared to the case where a matting agent is used, and at the same time, a texture is obtained, and a moist 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 constituting the matting layer. Examples of such resins 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). Therefore, the resin for forming the matting layer is preferably a resin that easily exhibits surface properties such as processing characteristics and abrasion resistance, and radiation-curable resins are preferred resins from these viewpoints. Since the content of the wrinkle-forming stabilizer contained in the matting layer of the present embodiment is extremely small, the performance of the resin for forming the matting layer is more directly exhibited as its surface property.

[0061] The radiation-curable resin is a resin having a radiation-curable functional group, and the radiation-curable functional group is a group that crosslinks and cures upon irradiation with radiation. Examples thereof preferably 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. In addition, 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 and 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 formation stabilizer and stably improving the matting effect, and improving the moist touch feeling, the ultraviolet ray-curable resin is preferable. Specifically, the radiation-curable resin can be appropriately selected and used from among polymerizable monomers and polymerizable oligomers that have been conventionally used as radiation-curable resins.

[0063] As the polymerizable monomer, a (meth)acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is more preferable. 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 moist touch feeling, 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 moist touch feeling. 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 oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth)acrylate oligomer, etc. may be mentioned. Furthermore, examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate-based oligomers having a (meth)acrylate group in the side chain of polybutadiene oligomer, silicone (meth)acrylate-based oligomers having a polysiloxane bond in the main chain, aminoplast resin (meth)acrylate-based oligomers obtained by modifying aminoplast resin having many reactive groups in a small molecule, and oligomers having a cation-polymerizable functional group in the molecule such as novolac-type epoxy resin, bisphenol-type epoxy resin, aliphatic vinyl ether, and aromatic vinyl ether.

[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 moist touch feeling, and further improving the 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 preferable, urethane (meth)acrylate oligomer and polycarbonate (meth)acrylate oligomer are more preferable, and urethane (meth)acrylate oligomer is even more preferable.

[0067] From the viewpoints of stabilizing the formation of wrinkles, steadily improving the matting effect, improving the moist touch feeling, and further improving the 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 the 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 the polymerizable monomer. As the polymerizable oligomer, a polyfunctional urethane (meth) acrylate oligomer is preferable, a polyfunctional urethane acrylate oligomer is more preferable, and as the polymerizable monomer, a polyfunctional polymerizable monomer is preferable, a polyfunctional (meth) acrylate monomer is more preferable, and a polyfunctional acrylate monomer is even more preferable. It is possible to stabilize the formation of wrinkles, stably improve the matte effect, improve the moist 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 above-mentioned wrinkle formation stabilizer in a predetermined content. The resin composition used in this embodiment may contain other components according to the desired performance 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 a plurality of types.

[0070] In addition, when the above resin is an ultraviolet curable resin that cures by ultraviolet rays, it is preferable to contain additives such as a photoinitiator and a photopolymerization 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-acyl oxime ester, thioxanthones, and the like. In addition, the photopolymerization accelerator can reduce the polymerization inhibition by air during curing and increase the curing rate. Examples thereof include one or more selected from isoamyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, and the like.

[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 resin and a wrinkle formation stabilizer by irradiating with light having a wavelength of at least 100 nm or more and 380 nm or less. It is characterized by that. 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 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 wavelength light, a laminate having the substrate and the matte layer can be manufactured. This forming method is suitable for forming a matte layer having a matte effect in which the 60° gloss value on the matte layer side is 20.0 or less, 10.0 or less, and even less, and having a moist touch.

[0072] The method for forming a matting layer according to this embodiment enables easy acquisition of a basic matting layer. Specifically, when forming the matting layer, ultraviolet light with a short wavelength of at least 100 nm or more and 380 nm or less is irradiated onto a resin composition for matting formation containing a wrinkle formation stabilizer for forming the matting layer, whereby wrinkles can be formed on at least one surface of the matting layer, and it becomes possible to impart a matting effect and a moist touch to the matting layer.

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

[0074] When short-wavelength ultraviolet light is irradiated onto a coating layer obtained by coating the resin composition for matting layer formation to a predetermined thickness, the energy of the ultraviolet light penetrates only the surface portion, and since the energy does not reach the lower layer, only the surface portion of the resin composition starts to cure. Therefore, it is considered that wrinkles are formed due to 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 matting layer formation is cured by irradiation with short-wavelength ultraviolet light. Also, from the comparison between the examples and comparative examples described later, 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 expressed to a sufficient extent over the entire surface of the matting layer, and a moist touch is not sufficiently expressed. Therefore, the stable expression of the matting effect and the moist touch cannot be explained only by the curing of only the surface portion by ultraviolet light 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 moist touch, it is essential that a wrinkle-forming stabilizer is included. Considering that a stable matting effect and a moist 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 of 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 moist 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 light 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 due to 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 progresses from the vicinity of the surface where the progress of curing is slow to the deep portion away in the depth direction, and the layer of the resin composition becomes a cured product, and thus 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 moist touch is constituted. From the viewpoint of promoting the progress of curing in the deep portion, as described later, 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 natural emission light or laser light with high coherence (interferability) by induced emission can be used, but usually natural 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 moist touch is also improved.

[0077] From the viewpoint of stabilizing the formation of wrinkles, stably improving the dulling effect, and improving the moist 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 this embodiment, from the viewpoint of stably improving the dulling effect and improving the moist touch, it is preferable to use light of a shorter wavelength, and it can be said that medium-wavelength ultraviolet rays (wavelength: 280 to 320 nm), 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 region of less than 200 nm.

[0078] In this embodiment, from the viewpoint of stabilizing the formation of wrinkles, stably improving the dulling effect, and improving the moist 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. Also, there is no particular limitation on the upper limit. 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. Also, 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 the present 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 contributing 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, or post-curing may be performed to further cure the resin composition after irradiation with light having a wavelength of 100 nm or more and 380 nm or less. Whether or not to employ pre-curing and post-curing may be appropriately determined according to the desired properties required for the matting layer (for example, surface properties such as processing characteristics and stain resistance). In addition, although the above-mentioned wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiations such as electron beams. For example, in post-curing, electron beams can be preferably used from the viewpoint of improving the surface properties of the matting layer.

[0080] In the forming method of the present 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 the 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 peelability 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 this embodiment may be a support with a thin thickness in micrometers or a support with a thick thickness of millimeter 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)acrylic acid methyl, poly(meth)acrylic acid ethyl, poly(meth)acrylic acid butyl, and (meth)acrylic acid methyl-(meth)acrylic acid butyl copolymer; polyamide resins typified 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 including oxidation method and 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. The release layer is preferably provided over the entire surface of the support in order to improve the peelability from the transfer layer. The release layer preferably contains a resin, and more preferably contains a resin and a release agent.

[0088] (Resin) 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, more preferably 90% by mass or more, more preferably 95% by mass or more, and even more 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 ratio of the cured product of the resin composition containing a curable resin 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, more preferably 90% by mass or more, more preferably 95% by mass or more, and even more 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 multiple types. Further, the resin composition containing a thermosetting resin may be one added with a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent.

[0092] Examples of the radiation-curable resin for the release layer include those exemplified as the radiation-curable resin for the matte 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 an organic group 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, examples of the organic group preferably include reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenolic 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. Among them, reactive functional groups are preferable, and particularly (meth)acrylic groups are preferable, that is, particularly (meth)acrylic-modified silicone oils are 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, still more preferably 1 to 2 parts by mass, based on 100 parts by mass of the resin forming the release layer. When the content of the release agent is within the above range, the 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. For this reason, it is preferable that the release layer has a predetermined thickness. The thickness of the release layer is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, 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, 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 thickness 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. More preferably, the transfer layer has a release layer and an adhesive layer in this order from the side of the releasable support. Further, 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 there are 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] Further, 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 antifogging 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 abrasion 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 abrasion resistance, the release layer preferably contains a cured product of a resin composition containing a curable resin as the resin. The ratio of the cured product of the resin composition containing a curable resin 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 that it is easy 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 that it is easy to further improve the abrasion resistance. Among them, the cured product of the resin composition containing an electron beam curable resin is preferable in that it can further improve the abrasion resistance and is easy 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 radiation-curable resin for the release layer include those exemplified as the resin composition containing the 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 it is preferably substantially free of said 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] The release layer preferably contains an ultraviolet absorber or a light stabilizer, and more preferably contains both an ultraviolet absorber and a light stabilizer in order to improve weather resistance. 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, in order to improve the handleability of the transfer sheet and the adhesion between the transfer layer and the adherend, a heat-sensitive adhesive layer is preferable. The heat-sensitive adhesive layer may also be called a heat-sealing layer.

[0111] When the adhesive layer is a pressure-sensitive adhesive layer, it is preferable that the adhesive layer contains an adhesive. 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 that the adhesive layer contains a thermosetting adhesive. The thermosetting adhesive preferably includes a composition having the property of undergoing a chemical reaction and crosslinking by heat. For example, examples include 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. The urethane resin constituting the two-component curable urethane adhesive is a polyurethane having a polyol (polyhydric alcohol) as the main component 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-based resins, vinyl acetate-based 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 two or more. 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 is improved, and it becomes easier 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 blue, 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 still 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 designability 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 kinds. Further, the binder resin may be those obtained by adding curing agents such as isocyanate-based curing agents and epoxy-based curing agents to these resins and subjecting them to crosslinking curing. 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 the acrylic monomer 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. Further, when the mass ratio of the acrylic component to the urethane component is within the above range, in the case where the release layer is made of a urethane acrylic resin such as a urethane (meth)acrylate oligomer, the interlayer adhesion with the release layer becomes good.

[0126] The primer layer preferably contains an antiblocking agent. Examples of the 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 size 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 size of the antiblocking agent is measured as the mass average value d50 in the particle size distribution measurement 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; etc. Examples of the pattern (design) expressed by the decoration layer include a wood grain pattern such as annual rings and vessel 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 frosted pattern; a matte pattern; a pattern formed by arranging a plurality of concave and convex stripes 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; etc.

[0132] As the ink used for the colored layer and the pattern layer, a mixture obtained by appropriately mixing 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 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, cellulose acetate resin, etc. 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. 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, depending on the type and content of the colorant contained, the thickness of the colored layer and the pattern layer is preferably 1.5 μm or more.

[0135] Examples of the metal thin film include thin films of single metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt; thin films of alloys containing two or more of the above metal elements; and the like. Examples of the alloy include brass, bronze, stainless steel, and the like. 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 liquid 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, or a comma coating method, 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 separated 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-described 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 the present specification, "matting" means that it is difficult to visually recognize gloss, and although it varies depending on the color tone of the transfer layer and the like, generally, if the 60° gloss value is 20.0 or less, preferably about 10.0 or less, it is 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 can be imparted by the transfer sheet of the present embodiment (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 releasable 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 level, although some differences occur if the color tones of both are the same.

[0140] Hitherto, for a cosmetic material exhibiting a dark color such as black, it has been possible to impart a visible excellent matting effect with a matting agent content in the matting layer such that the 60° gloss value is 20.0 or less, preferably 10.0 or less. "Dark color" means low lightness, for example, the CIE (International Commission on Illumination) L value measured in accordance with JIS Z8781-4:2013 * a * b * in the L * value in the color system (hereinafter sometimes simply referred to as "L * value").) is usually about 40 or less, preferably 30 or less. However, due to the use of a large amount of the matting agent, streaks and unevenness occur during the formation of the matting layer, so it cannot be easily manufactured, and there is also a problem that the strength of the matting layer decreases. Further, for cosmetic materials exhibiting color tones other than dark colors, there was a limit to the reduction of the 60° gloss value even when the matting layer contained a matting agent. Such a tendency becomes more prominent as the 60° gloss value becomes smaller. Therefore, in the conventional technology using a matting agent, it is necessary to suppress the amount of the matting agent used for reasons such as manufacturing, and thus it has been in a situation where a more excellent visible matting effect cannot be obtained.

[0141] In the present embodiment, when forming the basic matting layer, by combining and using two types of wrinkle-forming stabilizers having a predetermined average particle diameter and making the content thereof small as described above, not only has it been possible to stably obtain a visibly extremely excellent matting effect and texture, but also a moist touch has been obtained. Further, by suppressing the amount of the wrinkle-forming 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 matting 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 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 matting effect. Also, for decorative materials presenting color tones other than black or other dark colors, they can also have the above-mentioned 60° gloss value. In this specification, the 60° gloss value on the transfer layer side is 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 includes 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 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 oxidation method and roughening method can be applied to 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 surface 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 into contact with and overlapping the surface on the transfer layer side of the transfer sheet on 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 disposing 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, adhering the transfer layer of the transfer sheet and the resin, and forming a resin molded body. (z4) A step of taking out the resin molded body from the in-mold molding die.

[0148] In addition, 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 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 walls, furniture 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 for cabinets of home appliances, OA equipment, etc., 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 an uneven shape to these various members. Furthermore, in addition to the above various members, the decorative material can be used alone or in a form laminated or combined 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 an adherend, and at least a part of the surface of the transfer layer on the side opposite to the adherend has a surface shape in which Ssk (skewness) defined in ISO25178-2:2012 is less than 0.00.

[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 on the side 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 on the side opposite to the adherend 30 has a surface shape in which Ssk (skewness) is less than 0.00.

[0152] Examples of the adherend constituting the cosmetic material of the present embodiment include the adherends exemplified in the method for manufacturing the cosmetic material of the present embodiment. Examples of the transfer layer constituting the cosmetic 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 of the release layer side of the cosmetic 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 cosmetic 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×, 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 of the release layer side of the cosmetic material can be regarded as the surface shape of the release property support side of the transfer layer.

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

[0156] 1-3. Evaluation of texture before 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 carried out according to the following criteria. A: 18 or more people evaluated that the surface state was uniform and the visibility of the dulling effect was high. B: 15 or more and 17 or less people evaluated that the surface state was uniform and the visibility of the dulling effect was high. C: 14 or fewer people evaluated that the surface state was uniform and the visibility of the dulling effect was high.

[0157] 1-4. Evaluation of texture after weather resistance test Regarding the cosmetic materials obtained in the examples and comparative examples, the following weather resistance test was carried out. For 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 carried out using a weather resistance test device (trade name "Metal Weather" manufactured by Dipla Wintersteiger Co., Ltd.). In the weather resistance test, the following "ultraviolet irradiation process", "dew condensation process", and "water spray process" were taken as one cycle, and the cycle was repeatedly carried out 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] 1-5. Evaluation of a moist touch Regarding the cosmetic materials obtained in the examples and comparative examples, using silk fabric as the reference for the moist touch, 20 arbitrary adults were asked to evaluate the surface touch, and the evaluation was carried out according to the following criteria. A: 18 or more people evaluated that the touch was close to the reference and was a moist touch. B: More than 15 and less than 17 people evaluated that it had a texture close to the standard and a moist texture. C: 14 people or less evaluated that it had a texture close to the standard and a moist texture.

[0159] 2. Preparation of the matting layer [Matting layer 1] On one surface of a base material (a corona-discharge-treated PET sheet, thickness: 100 μm), a resin composition containing an acrylic resin and a urethane resin as binder resins was applied 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 - 100 mJ / cm 2 , nitrogen atmosphere (oxygen concentration 200 ppm or less)), then further irradiated with ultraviolet rays using a high-pressure mercury lamp (ultraviolet ray output density: 200 W / cm), and a laminate 1 having a matting layer 1 on the base material was obtained.

[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 · Wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass · Photoinitiator (benzophenone-based): 0.8 parts by mass

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

[0162] <Resin Composition 2 for Matte Layer Formation> · Polyfunctional urethane acrylate oligomer (tetrafunctional): 90 parts by mass · Monofunctional acrylate monomer: 10 parts by mass · Wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass · Wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass · Photoinitiator (benzophenone-based): 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 the matte layer 1, except that the resin composition 1 for matte layer formation was changed to the following resin composition 3 for matte layer formation.

[0164] <Resin Composition 3 for Matte Layer Formation> · Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Bifunctional acrylate monomer: 35 parts by mass · Photoinitiator (benzophenone-based): 0.8 parts by mass

[0165] [Matte Layer 4] A laminate 4 having a matte layer 4 on a substrate was obtained in the same manner as the matte layer 1, except that the resin composition 1 for matte layer formation was changed to the following resin composition 4 for matte layer formation and only irradiated with an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3 Mrad)).

[0166] <Resin Composition 4 for Matte Layer Formation> · Polyfunctional urethane acrylate oligomer (tetrafunctional): 65 parts by mass · Bifunctional acrylate monomer: 35 parts by mass · Matte agent (average particle diameter: 8.0 μm): 15.0 parts by mass · Photoinitiator (benzophenone-based): 0.8 parts by mass

[0167] 3. Preparation of Release Support, Transfer Sheet, and Decorative Material [Example 1] The laminate 1 produced above was used as the release support of Example 1. In the release support of Example 1, the matte layer 1 serves as a release layer. Next, the following resin composition 1 for forming a release layer was applied onto the release layer of the release support (onto the matte layer 1 of the release support) to form an uncured resin layer, and the uncured resin layer was cured by irradiating with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to form a release layer (thickness: 5 μm). Thereafter, corona irradiation was performed on the release layer. Next, the following resin composition for forming a primer layer was applied onto the corona-irradiated release layer and dried to form a primer layer with a thickness of 2.5 μm. Next, an acrylic resin (PMMA, weight average molecular weight: 96,000) was applied onto the primer layer and dried to form an adhesive layer having heat sealability 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.

[0168] The adhesive layer of the transfer sheet of Example 1 and one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC, trade name "Carbo Polish") as the adherend were opposed and laminated. 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 adhered to the adherend. Next, the release 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.

[0169] <Resin composition 1 for forming a release layer> · Ionizing radiation curable resin (bifunctional urethane acrylate oligomer): 100 parts by mass · Ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 479): 0.5 part by mass · Light stabilizer (manufactured by BASF, trade name: Tinuvin 123): 0.3 part by mass

[0170] <Resin composition for forming a primer layer> · Polycarbonate-based urethane acrylate copolymer: 100 parts by mass (Weight average molecular weight 50,000) · UV absorber (BASF, trade name: Tinuvin 479): 20 parts by mass · UV absorber (BASF, trade name: Tinuvin 400): 15 parts by mass · Light stabilizer (BASF, trade name: Tinuvin 123): 3.5 parts by mass · Anti-blocking agent (silica with an average particle diameter of 3 μm): 10 parts by mass · Solvent: appropriate amount

[0171] [Example 2] On one surface of a support (PET sheet subjected to corona discharge treatment. Thickness: 100 μm), a resin composition containing an acrylic resin and a urethane resin as binder resins was applied 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 dry)), and a laminate 2' having an easy-adhesion layer and an uncured release layer was obtained on the support. Next, the surface of the matting layer 2 side of the laminate 2 was dry-laminated onto the uncured coating film (uncured release layer) of the laminate 2', and a laminate 2'' was obtained. Next, the laminate 2'' was irradiated with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) from the PET side of the laminate 2' constituting the laminate 2'' to cure the uncured release layer. Next, the laminate 2 was peeled off from the laminate 2'', and a release support used in Example 2 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 2, a shape in which the surface shape of the matting layer 2 was inverted was shaped.

[0172] Next, the resin composition 1 for forming a release 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 release layer (thickness: 5 μm). Thereafter, corona irradiation was performed on the release layer. Next, the resin composition for forming the primer layer was applied onto the corona-irradiated release layer and dried to form a primer layer with a thickness of 2.5 μm. Next, an acrylic resin (PMMA, weight average molecular weight: 96,000) was applied onto the primer layer and dried to form an adhesive layer having a heat sealability 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 2.

[0173] The adhesive layer of the transfer sheet of Example 2 was opposed to and laminated with one surface of a polycarbonate plate (thickness: 2 mm, manufactured by AGC Inc., trade name "Carbo Polish") which is an adherend. Then, from the transfer sheet side, using a laminator (roll type thermal transfer machine manufactured by Navitas Co., Ltd., 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 adhered to the adherend. Next, the release support was peeled off from the laminate to obtain the decorative material of Example 2. The decorative material of Example 2 has a transfer layer on the adherend.

[0174] <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

[0175] [Example 3] The transfer sheet and decorative material of Example 3 were obtained in the same manner as in Example 1, except that the resin composition 1 for forming the release layer was changed to the resin composition 2 for forming the release layer described below.

[0176] <Resin composition 2 for forming 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: Tinuvin479): 2 parts by mass · Light stabilizer (Nippon Emulsion Co., Ltd., trade name: Sanol LS-3410): 3 parts by mass

[0177] [Comparative Examples 1-2] Except that laminate 2 was changed to laminates 3 to 4 when obtaining the release support, the release supports, transfer sheets, and decorative materials of Comparative Examples 1 and 2 were obtained in the same manner as in Example 2. On the release layer of the release support used in Comparative Examples 1 and 2, a shape in which the surface shape of the matting layer 3 to 4 is inverted is shaped.

[0178]

Table 1

[0179] 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 on the release layer side of the decorative material of 1.5 or 1.6, 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 a moist touch. On the other hand, although some wrinkles occurred on the surface of the decorative material obtained using the transfer sheet of Comparative Example 1 as shown in Fig. 8, the visibility of the matting effect could not be stably obtained, and although there were parts where the gloss value was the same as in the example, there were also parts with high gloss, and the surface state was unstable (not uniform), and it could not be said that it was excellent in texture. In addition, the decorative materials obtained using the transfer sheets of Comparative Examples 1 and 2 were both poor in a moist touch and rather had a rough touch.

[0180] Figure 7 is an optical microscope image of the release layer side of the decorative material obtained using the transfer sheets of Example 1 and Example 3 (the horizontal width of the image corresponds to 272.0 μm. The same applies to the horizontal widths of Figures 8 and 9). According to the optical microscope images (Figure 7) of Example 1 and Example 3, it can be confirmed that the decorative materials of the examples have irregular wrinkles on their surfaces. On the other hand, according to the optical microscope image (Figure 8) of Comparative Example 1, although some wrinkles have occurred on its surface and there are regions with wrinkles similar to those of the examples in part, the formation of wrinkles is unstable (not uniform) and it can be seen that they are mixed with regions without wrinkles. Also, according to the optical microscope image (Figure 9) of Comparative Example 2, wrinkles like those of the examples are not confirmed, and a convex shape corresponding to the contour shape of the matting agent is confirmed. The surface state is unstable (not uniform), and it cannot be said to have excellent texture.

Explanation of Symbols

[0181] 100: Transfer sheet 200: Decorative 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: Concave part 3: Convex part (protrusion)

Claims

1. A transfer sheet having a transfer layer on a releasable support, at least a part of the surface of the transfer layer on the side of the releasable support has a surface shape defined in ISO 25178-2:2012 with Ssk (skewness) less than 0.00, 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 Sku (kurtosis) defined in ISO 25178-2:2012 of the surface shape is 3.00 or more.

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

4. The transfer sheet according to any one of claims 1 to 3, wherein Rz (maximum height), which is a parameter of the peak and height of the contour curve defined in JIS B0601:2013 of the surface shape, is 3.00 μm or more.

5. The transfer sheet according to any one of claims 1 to 4, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve defined in JIS B0601:2013 of the surface shape, is 2.00 μm or less.

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

7. The transfer sheet according to claim 6, 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.

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

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

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

11. The transfer sheet according to any one of claims 8 to 10, wherein the release layer contains an ultraviolet absorber or a light stabilizer.

12. The transfer sheet according to any one of claims 8 to 11, wherein the release layer substantially does not contain particles.

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

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

15. 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 according to any one of claims 1 to 14 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.

16. 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 less than 0.00, and the 60° gloss value of the part having the surface shape is 10.0 or less.

Images