Decorative sheet, method for producing decorative sheet and decorative material

Abstract

To provide a decorative sheet having good tactile feeling, low-glare properties and visibility of a design while having good matting properties.SOLUTION: There is provided a decorative sheet 10 having a base material layer 1 and a matte layer 2, wherein a first surface of the matte layer on the opposite side from the base material layer has a surface shape having wrinkle structures X and embossed parts Y which are recessed toward the base material layer side from the bottoms of recessed parts 5 of the wrinkle structures in the thickness direction, when viewed from the thickness direction, the plurality of embossed parts extend in a first direction, in a second direction orthogonal to the first direction, the maximum height (Rz) of the first surface is 15 μm or more and 100 μm or less and in the first direction, the 45-degree reflection intensity of the first surface by a goniophotometer is 0.50 or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a decorative sheet, a method for manufacturing a decorative sheet, and a decorative material. [Background technology]

[0002] Decorative sheets used in decorative materials may be required to have a matte finish, for example, to improve design. For example, Patent Document 1 discloses a decorative sheet having a pattern layer and a concealing layer on one side of a base sheet, and a gloss-adjusting layer (matte layer, gloss layer) on the other side. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-062081 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have found that providing a matte layer having a wrinkled structure can impart a good matte property (low gloss) to a decorative sheet, compared to, for example, providing a matte layer containing a filler. On the other hand, from the viewpoint of improving the functionality of decorative sheets, the matte layer may be required to have not only good matte property but also good tactile feel, good low glare, and good visibility of the design.

[0005] The present disclosure has been made in view of the above problems, and has as its main object to provide a decorative sheet that has good matte properties, good tactile feel, low glare, and good design visibility. [Means for solving the problem]

[0006] The present disclosure provides a decorative sheet having a base layer and a matte layer, wherein a first surface of the matte layer opposite the base layer has a surface shape having a wrinkled structure and embossed portions that are recessed in the thickness direction toward the base layer from the bottom of the recesses of the wrinkled structure, and when viewed from the thickness direction, the plurality of embossed portions extend in a first direction, and in a second direction perpendicular to the first direction, the maximum height (Rz) of the first surface is 15 μm or more and 100 μm or less, and the 45° reflection intensity of the first surface in the first direction as measured by a goniophotometer is 0.50 or less.

[0007] The present disclosure also provides a method for producing the above-mentioned decorative sheet, comprising a matte layer-forming step of forming the matte layer on one side of the base layer, wherein the matte layer-forming step comprises a wrinkle structure-forming process of applying a curable resin composition for the matte layer to one side of the base layer to form a coating layer, and curing the coating layer by irradiating with ionizing radiation, thereby forming a precursor layer having the wrinkle structure; and an embossed portion-forming process of embossing the surface of the precursor layer on the wrinkle structure side to obtain the matte layer, wherein the irradiation with ionizing radiation in the wrinkle structure-forming process comprises (1) an irradiation process with light of a first wavelength of 100 nm or more and less than 200 nm, and (2) at least one of an electron beam irradiation process and an irradiation process with light of a second wavelength of 200 nm or more and 400 nm or less, performed in this order.

[0008] The present disclosure also provides a decorative material having an adherend and a decorative sheet, wherein the decorative sheet is the decorative sheet described above. [Effects of the Invention]

[0009] The present disclosure has the effect of providing a decorative sheet that has good matte properties, good tactile feel, low glare, and good design visibility. [Brief explanation of the drawings]

[0010] [Figure 1]1 is a schematic cross-sectional view illustrating a decorative sheet according to the present disclosure. [Figure 2] 1 is a schematic cross-sectional view illustrating a decorative sheet according to the present disclosure. [Figure 3] 1 is a microscopic image illustrating a wrinkle structure according to the present disclosure. [Figure 4] FIG. 2 is a schematic plan view illustrating a first direction and a second direction in the present disclosure. [Figure 5] 1 is a schematic cross-sectional view illustrating a decorative sheet according to the present disclosure. [Figure 6] FIG. 1 is a flow diagram illustrating a method for producing a decorative sheet according to the present disclosure. [Figure 7] 1 is a schematic cross-sectional view illustrating a decorative material according to the present disclosure. [Figure 8] 1 is a graph showing the relationship between the light-receiving angle and the normalized reflection intensity BSS for the decorative sheet obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] Below, embodiments will be described with reference to the drawings etc. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. Furthermore, to make the explanation clearer, the drawings may show the width, thickness, and shape of each part schematically compared to the actual form, but this is merely an example and should not be interpreted as limiting.

[0012] In this specification, when describing a mode in which another component is placed on a certain component, the term "above" or "below" is used, unless otherwise specified, to include both a case in which another component is placed directly above or below a certain component so as to be in contact with the component, and a case in which another component is placed above or below a certain component with another component interposed therebetween. Also, in this specification, when describing a mode in which another component is placed on the surface of a certain component, the term "on the surface" or "on the surface side" is used, unless otherwise specified, to include both a case in which another component is placed directly above or below a certain component so as to be in contact with the component, and a case in which another component is placed above or below a certain component with another component interposed therebetween.

[0013] In addition, in this specification, the terms "plate," "sheet," and "film" are not distinguished from one another solely based on differences in name. For example, a "sheet" also includes a member called a "plate" or a "film."

[0014] The decorative sheet, the method for manufacturing the decorative sheet, and the decorative material according to the present disclosure will be described in detail below.

[0015] A. Decorative sheet The decorative sheet of the present disclosure is a decorative sheet having a base layer, a decorative layer, and a matte layer, in that order in the thickness direction, wherein a first surface of the matte layer opposite the base layer has a surface shape having a wrinkled structure and embossed portions that are recessed toward the base layer in the thickness direction from the bottom of the recesses of the wrinkled structure, and when viewed from the thickness direction, the multiple embossed portions extend in the first direction, and in a second direction perpendicular to the first direction, the maximum height (Rz) of the first surface is within a predetermined range, and in the first direction, the 45° reflection intensity of the first surface measured with a goniophotometer is within a predetermined range.

[0016] 1 and 2 are schematic cross-sectional views illustrating decorative sheets according to the present disclosure. In the decorative sheet 10 shown in FIG. 1, the substrate layer 1 and the matte layer 2 are T2, the base layer 1, the decorative layer 3, and the matte layer 2 are laminated in the thickness direction D. T 1 and 2, the first surface S1 of the matte layer 2 has a wrinkle structure X having protrusions 4 and recesses 5, and a thickness direction D T and an embossed portion Y recessed toward the base layer 1 side from the bottom of the recessed portion 5 of the wrinkle structure X.

[0017] FIG. 3 is a microscope image illustrating a wrinkle structure according to the present disclosure. As shown in FIG. 3, wrinkle structure X has an uneven shape due to irregular wrinkles. The irregular wrinkles have multiple protrusions 4 formed by multiple protrusions and multiple recesses 5 formed by being surrounded by the multiple protrusions. Meanwhile, FIG. 4 is a schematic plan view illustrating the first and second directions according to the present disclosure. The decorative sheet 10 shown in FIG. 4 has a wood grain pattern including an annual ring pattern 20 and a vascular pattern 21. Note that the annual ring pattern 20 includes not only a strict annual ring pattern but also a cross grain pattern and a straight grain pattern composed of annual rings. Since the vascular pattern 21 is usually arranged along the extension direction of the annual ring pattern 20, when embossed portions (not shown) are arranged in sync with the vascular pattern 21, the multiple embossed portions are arranged to extend along one direction (the same direction as the extension direction of the annual ring pattern 20 in FIG. 4). In the present disclosure, the thickness direction D T When viewed from the outside, the extension direction of the multiple embossed portions is defined as a first direction D1, and the direction perpendicular to the first direction D1 is defined as a second direction D2. In the present disclosure, in the second direction D2, the maximum height (Rz) of the first surface of the matte layer is within a predetermined range, and in the first direction D1, the 45° reflection intensity of the first surface of the matte layer measured with a goniophotometer is within a predetermined range.

[0018] According to the present disclosure, by ensuring that the maximum height (Rz) and 45° reflection intensity are within a predetermined range, a decorative sheet can be obtained that has good matte properties while also having good tactile feel, low glare, and good design visibility. As described above, the present inventors have discovered that providing a matte layer with a wrinkled structure can impart good matte properties (low gloss) to a decorative sheet, compared to, for example, providing a matte layer containing an added filler. Furthermore, while forming a wrinkled structure in the matte layer can provide a silky, smooth tactile feel, there are cases where a stronger tactile feel is required. Furthermore, from the perspective of improving the functionality of decorative sheets, there are cases where the matte layer is required to not only have good matte properties, but also good tactile feel, good low glare, and good design visibility at the same time.

[0019] Therefore, the present inventors investigated the provision of an embossed portion on a matte layer having a wrinkled structure. They then discovered that by adjusting the maximum height (Rz) and 45° reflection intensity within a predetermined range, not only good matte properties but also good tactile feel, good low glare, and good visibility of the design could be simultaneously obtained, leading to the present disclosure. In particular, while providing an embossed portion facilitates a stronger tactile feel, if the embossed portion's traces are visible, they may impair the visibility of the design. In contrast, the present disclosure achieves both a good tactile feel and good visibility of the design by adjusting the embossed portion's traces to a level where they are not visible, while still providing a good tactile feel.

[0020] Furthermore, for example, when a decorative sheet is placed on a floor and the setting sun shines through a window, the matte layer of the decorative sheet placed on the floor may glare. A decorative sheet with a matte layer having a wrinkled structure has better matte properties than conventional sheets, so the gap when glare occurs is more easily perceived. Therefore, decorative sheets with a matte layer having a wrinkled structure are required to have better low-glare properties than conventional sheets. In the present disclosure, good low-glare properties can be obtained by reducing the 45° reflection intensity of the first surface measured with a goniophotometer.

[0021] 1.Matte layer The decorative sheet of the present disclosure has a matte layer on one side of a substrate layer, and the first side of the matte layer has a surface shape with a wrinkle structure and embossed portions.

[0022] (1) Maximum height Rz In the present disclosure, the maximum height (Rz) of the first surface of the matte layer is measured along the second direction, which is a direction perpendicular to the first direction in which the embossed portions extend as viewed from the thickness direction, and allows for accurate evaluation of the effects of the embossed portions (e.g., the effects of the embossed portions on the tactile feel and embossed marks).

[0023] In the second direction, the maximum height (Rz) of the first surface is typically 15 μm or more, and may be 17 μm or more, or 19 μm or more. If Rz is too small, the good tactile feel resulting from the embossed portion may not be perceived. On the other hand, in the second direction, the maximum height (Rz) of the first surface is typically 100 μm or less, and may be 95 μm or less, or 90 μm or less. If Rz is too large, the traces of the embossed portion are easily visible, and the traces may impair the visibility of the design.

[0024] The maximum height (Rz) of the first surface is a value specified in JIS B0601:2013. Rz is one of the parameters for the peak and height of a profile curve, and is the sum of the height of the highest peak and the depth of the deepest valley within the profile curve over a reference length. The larger the Rz value, the more likely it is that a convex portion with a larger (higher) shape is present relative to the valley (concave portion), and this is an indicator of the tendency for a large number of such convex portions to be present. When measuring the Rz (maximum height) of the first surface, the cutoff value was 0, and the measurement magnification was 10x. By using a measurement magnification of 10x, which is lower than conventional methods, the effect of the wrinkle structure on Rz is reduced, allowing for a more accurate evaluation of the effect of the embossed portion on Rz.

[0025] Methods for adjusting the maximum height (Rz) of the first surface include, for example, changing the embossing shape of the embossing plate, adjusting the temperature during embossing, adjusting the lamp irradiation intensity when forming the wrinkle structure, and adjusting the material of the coating layer that forms the wrinkle structure.

[0026] (2) Reflection intensity measured by a goniophotometer In the present disclosure, the surface shape of the first surface of the matte layer can be identified by the 45° reflection intensity and 75° reflection intensity of the first surface measured using a goniophotometer.

[0027] (i) 45° reflection intensity The 45° reflection intensity of the first surface of the matte layer is measured along a first direction, which is the direction in which the embossed portions extend as viewed from the thickness direction, and allows for accurate evaluation of the influence of the embossed portions (for example, the influence of the embossed portions on glare).

[0028] In the first direction, the 45° reflection intensity of the first surface measured by a goniophotometer is typically 0.50 or less, and may be 0.45 or less, or even 0.40 or less. If the 45° reflection intensity is too high, there is a possibility that glare may be strong. On the other hand, in the first direction, the 45° reflection intensity of the first surface measured by a goniophotometer is, for example, 0.01 or more.

[0029] The 45° reflection intensity of the first surface is measured using a goniophotometer. The 45° reflection intensity corresponds to the reflection intensity at +45 degrees when visible light (light with a wavelength of 380 nm or more and 780 nm or less) is incident at an angle of -45 degrees relative to the normal direction of the first surface. The goniophotometer may be, for example, a GP-200 goniophotometer manufactured by Murakami Color Research Laboratory Co., Ltd. The goniophotometer is also called a goniophotometer. Details of how to determine the 45° reflection intensity will be described in the Examples below.

[0030] The 45° reflection intensity of the first surface can be adjusted by, for example, adjusting the particle size or amount added, adjusting the lamp irradiation intensity when forming the wrinkled structure, or adjusting the material of the coating layer that forms the wrinkled structure. For example, the 45° reflection intensity tends to be higher when the matting effect of the particles is greater. Furthermore, the 45° reflection intensity tends to be higher when the wrinkles in the wrinkled structure are unevenly distributed or are few in number, resulting in many flat areas without wrinkles.

[0031] (ii) 75° reflection intensity In the first direction, the 75° reflection intensity of the first surface of the matte layer measured by a goniophotometer is D SS1 In addition, in the second direction, the 75° reflection intensity of the first surface of the matte layer measured with a goniophotometer is defined as D SS2 Also, D SS1 and D SS2 The absolute value of the difference between SSX In this disclosure, D SSX / D SS1 is preferably 0.06 or less. This is because a decorative sheet with a highly uniform glare can be obtained. In other words, a decorative sheet with little change in glare can be obtained even when the viewing direction is changed. D SSX / D SS1 may be 0.05 or less, or may be 0.04 or less.

[0032] The 75° reflection intensity of the first surface is measured using a goniophotometer. The 75° reflection intensity corresponds to the maximum reflection intensity when visible light (light with a wavelength of 380 nm or more and 780 nm or less) is incident at an angle of -75 degrees relative to the normal direction of the first surface. The goniophotometer may be, for example, a goniophotometer GP-200 manufactured by Murakami Color Research Laboratory Co., Ltd. Details of how to determine the 75° reflection intensity are described in the examples below.

[0033] D SSX / D SS1 The method for adjusting D can be, for example, a method for adjusting the depth of the embossed portion or a method for adjusting the area of ​​the embossed portion. SSX / D SS1 In addition, assuming that the total area of ​​multiple embossed parts is constant, if the area of ​​each embossed part is reduced, the value of D SSX / D SS1 The value tends to be smaller.

[0034] (3) Embossed section The first surface of the matte layer has embossed portions recessed toward the base layer from the bottom of the recesses of the wrinkled structure described below. Furthermore, when viewed from the thickness direction, the plurality of embossed portions extend in the first direction.

[0035] Here, "plurality of embossed portions extending in the first direction" refers to the following state. That is, when the shape of the embossed portions is linear, if an embossed portion whose length extending in the first direction is 1.2 times or more longer than its length extending in the second direction is defined as a specific embossed portion, then "plurality of embossed portions extending in the first direction" refers to a state in which the specific embossed portions account for 20% or more of all embossed portions. Also, when the shape of the embossed portions is dot-like, one embossed portion (embossed portion aggregate) may be made up of a plurality of fine dots. When an embossed portion aggregate whose length extending in the first direction is 1.2 times or more longer than its length extending in the second direction is defined as a specific embossed portion aggregate, then "plurality of embossed portions extending in the first direction" refers to a state in which the specific embossed portions account for 20% or more of all embossed portion aggregates.

[0036] When the decorative layer has a pattern layer, the embossed portions are preferably arranged in a manner that synchronizes with the pattern layer. "Synchronization" means that the shapes and positions of the two target patterns generally match. Specifically, this means that the shape and position of the pattern of the embossed portions and at least some of the pattern of the pattern layer match to an extent that does not impair realism or luxury.

[0037] The shape of the embossed portions is not particularly limited, and examples thereof include lines and dots. When the embossed portions are linear, the extension direction of the linear embossed portions is preferably parallel to the first direction described above. In the present disclosure, "parallel" means that the angle between the two directions is 30° or less. The width of the embossed portions is, for example, 5 μm or more and 600 μm or less, or may be 10 μm or more and 500 μm or less. The width of the embossed portions refers to the length of the embossed portions in the second direction described above. The pitch of the embossed portions is, for example, 5 μm or more and 5000 μm or less, or may be 10 μm or more and 4000 μm or less. The pitch of the embossed portions refers to the shortest distance between adjacent embossed portions in the second direction described above. The width and pitch of the embossed portions are average values ​​of measurements at 10 or more points.

[0038] At least a portion of the embossed portion is typically located within the area surrounded by the outer edge of the wrinkle structure. The entire embossed portion may be located within the area surrounded by the outer edge of the wrinkle structure. The embossed portion may also be a portion recessed 10 μm or more from the reference plane of the wrinkle structure toward the decorative layer in the thickness direction. That is, the point recessed 10 μm from the reference plane of the wrinkle structure toward the decorative layer in the thickness direction may be used as the boundary, and the portion recessed from this boundary toward the decorative layer may be considered to be the embossed portion. It is also preferable that the bottom of the recess in the wrinkle structure is located on the opposite side of the decorative layer from the boundary.

[0039] The reference plane of the wrinkle structure is defined as follows: the plane whose normal direction is the thickness direction and which includes a point (position) corresponding to the median value of the height distribution in the uneven shape of the wrinkle structure.

[0040] The embossing ratio is the ratio of the area of ​​the embossed portion to the total area of ​​the wrinkle structure and the area of ​​the embossed portion on the first surface of the matte layer, as viewed in the thickness direction. The embossing ratio is, for example, 5% or more and 95% or less. If the embossing ratio is too low, a good tactile feel may not be obtained. On the other hand, if the embossing ratio is too high, the traces of the embossed portion may be easily visible. The embossing ratio may be 7% or more, or may be 10% or more. On the other hand, the embossing ratio may be 90% or less.

[0041] (4) Shape of wrinkle structure The wrinkle structure preferably has an uneven shape due to irregular wrinkles. The irregular wrinkles preferably have a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions. Furthermore, the protrusions preferably have linear protrusions.

[0042] In this specification, "linear protrusions" means that the ratio of the length to the width of the protrusions (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more. The method for determining the length and width of the protrusions is as described below. Hereinafter, linear protrusions may be referred to as linear protrusions.

[0043] A specific example of the wrinkle structure is shown in Fig. 3. Fig. 3 also shows that the surface shape of the first surface S1 of the matte layer 2 has irregular wrinkles in a planar view; that the irregular wrinkles have a plurality of convex portions 4 formed by a plurality of curved linear protrusions and a concave portion 5 formed by being surrounded by the plurality of protrusions (a plurality of convex portions 4); and that at least a portion of the curved convex portions 4 are each formed by a meandering linear protrusion, and that the meandering concave portion 5 is formed so as to be surrounded by the meandering linear protrusions. The matte effect is improved by the surface shape of the matte layer having a wrinkle structure formed by irregular wrinkles as shown in Fig. 3.

[0044] Here, "curved" means that there is one or more portions where the extension direction of the continuous linear protrusions 4 is reversed from one side to the other in a planar view. Hereinafter, a portion where the extension direction of the continuous linear protrusions 4 is reversed from one side to the other may be referred to as an "inverted portion." An example of an inverted portion is a shape that has an inflection point when the linear protrusions 4 are approximated by a continuous curve when the width of the planar view shape is ignored (when the width is considered to be 0). Another example of an inverted portion is a shape that has a portion that is approximated by a V-shaped folded line or two sides of a triangle sandwiching one vertex when the linear protrusions 4 are approximated by a straight line when the width of the planar view shape is ignored.

[0045] Furthermore, "meandering" means that there are two or more inverted portions in a plan view, and when the linear protrusions 4 are followed in their extending direction, the extending direction of the linear protrusions 4 alternately inverts in opposite directions at two adjacent inverted portions. For example, when the width of the planar shape of the linear protrusions 4 is ignored and the linear protrusions 4 are approximated by a continuous curve, examples of such an embodiment include a shape having a portion approximated by the Roman letter "S." Furthermore, when the width of the planar shape of the linear protrusions 4 is ignored and the linear protrusions 4 are approximated by a straight line, examples of such an embodiment include a shape having a portion approximated by the Roman letter "W."

[0046] In this specification, "irregular" means a shape that does not have a fixed rule, or is not arranged according to a fixed rule, i.e., is not patterned. A typical example of a non-irregular shape (regular shape) is a shape that is arranged with a fixed periodicity in a specific direction, such as a so-called lenticular lens, in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction. Therefore, in the present disclosure, the irregular wrinkles that may be present in the wrinkle structure that forms the surface shape of the matte layer include the fact that the shape of a single protrusion itself is irregular, not a shape formed according to a fixed rule such as periodicity; the fact that the shapes of multiple convex portions formed by multiple protrusions are irregular, not formed and arranged according to a fixed rule; and the fact that the shape of a concave portion surrounded by such multiple protrusions is also irregular.

[0047] In the wrinkle structure that forms the surface shape, if any of the shape of a single protrusion (a single convex portion), the shape and arrangement of each of the multiple protrusions (multiple convex portions), and the shape of a concave portion surrounded by the multiple protrusions is irregular, the surface of the matte layer is likely to have a specific surface shape.For the same reason, it is more preferable that all of them are irregular.

[0048] As described above, the surface of the matte layer has a wrinkled structure, essentially forming an uneven shape. The convex and concave portions in the uneven shape are defined based on the median value of the height distribution of the concave and convex shape, with regions with heights exceeding the median value being defined as convex portions and regions with heights equal to or less than the median value being defined as concave portions. For example, by utilizing the density difference (i.e., brightness difference) of an image having a density that corresponds 1:1 to the surface height of the matte layer, the darkest portion of the density distribution image can be designated as gradation 255, and the lightest portion of the density distribution image can be designated as gradation 0. For gradations 0 to 255, binarization processing can be performed to classify the image as concave portions with gradations 0 to 127 and convex portions with gradations 128 to 255. In this case, the median density value for the median height value is 127.

[0049] Furthermore, as shown in Fig. 3, for example, the wrinkle structure preferably has a plurality of convex portions formed by a plurality of protrusions that are irregular but have a certain degree of uniformity, and a concave portion surrounded by the convex portions. Therefore, in the convex portions (protrusions) shown in Fig. 3, a shape in which the width of the convex portions or the height of the convex portions changes drastically is not considered to be a preferable embodiment for obtaining a matte effect. Specific embodiments of the shapes of the wrinkles that constitute the wrinkle structure, i.e., the shapes of the convex portions (protrusions) and concave portions, that may be effective in improving the matte effect will be described below.

[0050] The shape of the recess may be acute-angled, semicircular, semielliptical, or a combination thereof in cross section. Furthermore, the shape of the recess may be a shape in which one protrusion has a recess in a part in cross section.

[0051] On the other hand, the shape of the convex portion can have a semicircular or semielliptical shape in cross section, although the width may vary.

[0052] The height of the convex portions (height of the protrusions) is, for example, 0.5 μm or more, and may be 1 μm or more, and the height of the convex portions is, for example, 10 μm or less.

[0053] The depth of the recess is, for example, 0.5 μm or more, and may be 1 μm or more, and the depth of the recess is, for example, 10 μm or less.

[0054] The distance from the top of the convex portion to the bottom of the concave portion (height difference between the convex portion and the concave portion) is, for example, 1 μm or more, and may be 2 μm or more. Furthermore, the distance is, for example, 24 μm or less, and may be 22 μm or less, or may be 20 μm or less. When the distance is within the above range, the matte effect is improved.

[0055] Here, the dimensions of the convex portions are the average values ​​of 10 convex portions (protrusions) at 10 arbitrary locations (100 μm square area × 10 locations) on the surface of the matte layer, that is, a total of 100 convex portions. The height of one convex portion (protrusion) is the average value of the heights of five arbitrary locations on one convex portion (protrusion).

[0056] The dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion.

[0057] The proportion of the convex portions is, for example, 15% or more, or may be 20% or more, or 30% or more. The proportion of the convex portions is, for example, 80% or less, or may be 70% or less, or may be 60% or less. When the proportion of the convex portions is within the above range, the surface of the matte layer is likely to have a specific surface shape in relation to the proportion of the concave portions surrounded by the convex portions, and the matte effect is improved.

[0058] Here, the occupancy ratio of the convex portions is the average value of the occupancy ratio of the convex portions at 10 arbitrary locations (100 μm square area×10 locations) on the matte layer.

[0059] The convex portions and concave portions may have portions of approximately the same direction and width, but the length of such portions is preferably short. When the length is short, the surface of the matte layer is more likely to have a specific surface shape, improving the matte effect. Specifically, the length of the continuation of convex portions and concave portions of approximately the same direction and width is, for example, 95 μm or less, or may be 80 μm or less, or may be 70 μm or less. Furthermore, the length is, for example, 5 μm or more, or may be 10 μm or more, or may be 15 μm or more. When the length is within the above range, the wrinkles become more irregular, improving the matte effect.

[0060] Here, it is preferable that 80% or more of any 10 convex portions and concave portions (i.e., a total of 100 convex portions and concave portions) in any 10 locations (100 μm square area × 10 locations) on the matte layer satisfy the above condition. The above proportion may be 85% or more, 90% or more, or 95% or more.

[0061] In this specification, the term "substantially the same" means that the directions are roughly the same, without branching, and the direction is within ±3°, and the width is within ±5%.

[0062] The number of convex portions (protrusions) in a 100 μm square area is, for example, 10 or more, or may be 20 or more, or may be 30 or more. The number of convex portions is, for example, 200 or less, or may be 100 or less, or may be 70 or less. When the number of convex portions is within the above range, the surface of the matte layer is likely to have a specific surface shape, and the matte effect is improved.

[0063] Here, the number of convex portions in a 100 μm square area is the average value of the number of convex portions in 10 places (100 μm square area×10 places) on the matte layer.

[0064] The surface of the matte layer preferably has a wrinkled structure at least in part, and more preferably has a wrinkled structure over the entire surface.

[0065] In the surface shape of the matte layer in the present disclosure, the wrinkle structure preferably has the following surface properties.

[0066] (5) Surface characteristics of wrinkle structure The wrinkled structure preferably has the following surface properties: The surface properties of the wrinkled structure are controlled by adjusting the type of material used in the matte layer, the thickness of the matte layer, and the conditions of the irradiation treatment described below.

[0067] (i) Spc (arithmetic mean curvature of the apex of the protrusion) The Spc (arithmetic mean curvature of the apex of the protrusion) of the wrinkle structure specified in ISO 25178-2:2021 is, for example, 27,000 mm -1 is less than 26000mm -1 May be less than 25,000 mm -1 On the other hand, the Spc (arithmetic mean curvature of the apex of the protrusion) may be, for example, 1000 mm -1 Above 1200mm -1 It may be more than 1400mm -1 It may be more than that.

[0068] Spc (arithmetic mean curvature of protrusion apex) is one of the three-dimensional surface texture parameters specified in ISO 25178-2:2021, and is the average curvature (average sharpness) of the tip of the peak, calculated from the arithmetic mean value of the curvature radius of the peak (peak of protrusion) of the part classified as a mountain (convex part) in the feature image included in the reference area. Therefore, Spc (arithmetic mean curvature of protrusion apex) is the reciprocal (mm -1 )

[0069] The larger the value of Spc (arithmetic mean curvature of the apex of the protrusion), the greater the curvature of the tip of the peak (convex portion) (the reciprocal of which is the smaller the radius of curvature, and the sharper the shape of the tip). On the other hand, the smaller the value of Spc (arithmetic mean curvature of the apex of the protrusion), the smaller the curvature of the apex of the protrusion (the reciprocal of which is the larger the radius of curvature, and the blunter the shape of the tip). In other words, the smaller the Spc (arithmetic mean curvature of the apex of the protrusion), the more rounded the protrusion is, and the closer it is to a flat surface, which reduces the matte effect of the matte layer of the decorative sheet.

[0070] In this specification, the cutoff value for measuring Spc (arithmetic mean curvature of the apex of the protrusion) is 0. In addition, in this specification, Spc (arithmetic mean curvature of the apex of the protrusion) is the average value of measurements taken at any 10 points.

[0071] (ii) Rz (maximum height) The wrinkle structure has a maximum height Rz (maximum height) of, for example, 24.0 μm or less, or alternatively, 22.0 μm or less, or 20.0 μm or less, as defined in JIS B0601:2013. On the other hand, the maximum height Rz (maximum height) is, for example, 2.0 μm or more, or alternatively, 2.2 μm or more, or alternatively, 2.5 μm or more.

[0072] As mentioned above, Rz (maximum height) is one of the parameters of the peak and height of the contour curve. When measuring the (maximum height) of the wrinkle structure, the cutoff value is 0. Furthermore, Rz (maximum height) of the wrinkle structure is the average value of the measurements at any 10 points.

[0073] (iii) Ra (arithmetic mean roughness) The Ra (arithmetic mean roughness) of the wrinkle structure as defined in JIS B0601:2013 is, for example, 5.0 μm or less, or alternatively, 4.8 μm or less, or 4.5 μm or less, while the Ra (arithmetic mean roughness) is, for example, 0.1 μm or more, or alternatively, 0.2 μm or more, or alternatively, 0.3 μm or more.

[0074] Ra (arithmetic mean roughness) is one of the parameters in the height direction of a profile curve, and is the average difference in height from the average surface on a profile curve over a reference length. The smaller the Ra (arithmetic mean roughness) value, the smaller the difference in height between the convex parts in the wrinkle structure and the concave parts that form accordingly, and is an indicator that indicates a tendency for the shape to become smoother and more uniform.

[0075] In the measurement of Ra (arithmetic mean roughness) in this specification, the cutoff value is 0. Furthermore, in this specification, the Ra (arithmetic mean roughness) is the average value of measurements taken at any 10 points.

[0076] (iv) RSm (average length of curved elements) The RSm (average length of curved elements) of the wrinkle structure as defined in JIS B0601:2013 is, for example, 150 μm or less, or alternatively, 130 μm or less, or 120 μm or less, while the RSm (average length of curved elements) is, for example, 2 μm or more, or alternatively, 4 μm or more, or alternatively, 8 μm or more.

[0077] RSm (average length of curve elements) is a horizontal parameter of the profile, and is the average length of the profile elements in the reference length. The smaller RSm, the more convex parts are included in the reference length.

[0078] In this specification, when measuring RSm (average length of curved line elements), the cutoff value is 0. In addition, in this specification, RSm (average length of curved line elements) is the average value of measurements taken at any 10 points.

[0079] (v) Sa (arithmetic mean height) The wrinkle structure's Sa (arithmetic mean height) as defined in ISO 25178-2:2021 is, for example, 2.5 μm or less, and may be 2.0 μm or less, or 1.5 μm or less. Meanwhile, the Sa (arithmetic mean height) is, for example, 0.1 μm or more, and may be 0.3 μm or more. The Sa (arithmetic mean height) is an index showing the state of undulations across the entire surface of the wrinkle structure.

[0080] In the present specification, the cutoff value for measuring Sa (arithmetic mean height) is 0. In addition, in the present specification, Sa (arithmetic mean height) is the average value of measurements taken at any 10 points.

[0081] (vi) Ssk (Skewness) The Ssk (skewness) of the wrinkle structure defined in ISO 25178-2:2021 is, for example, 1.5 μm or less, and may be 1.0 μm or less. On the other hand, the Ssk (skewness) is, for example, −0.8 μm or more, and may be −0.6 μm or more.

[0082] Ssk (skewness) is an index that indicates the degree of deviation of the height distribution from the average plane. When Ssk is 0, the surface shape is symmetrical (normal distribution) with respect to the average plane, and when Ssk exceeds 0, the surface shape is biased downward from the average plane, i.e., toward the lower height side, and the protrusions tend to be sharp and thin near their peaks. On the other hand, when Ssk is less than 0, the surface shape is biased upward from the average plane, i.e., toward the higher height side, and the protrusions tend to be blunt and thick near their peaks.

[0083] In the measurement of Ssk (skewness) in this specification, the cutoff value is 0. Furthermore, in this specification, Ssk (skewness) is the average value of measurements taken at any 10 points.

[0084] (vii) Sku (Kurtosis) The Sku (kurtosis) of the wrinkle structure defined in ISO 25178-2:2021 is, for example, 4.0 or less, or may be 3.7 or less, or may be 3.5 or less. On the other hand, the Sku (kurtosis) is, for example, 0.1 or more, or may be 0.3 or more, or may be 0.5 or more.

[0085] Sku (kurtosis) is one of the three-dimensional surface texture parameters specified in ISO25178-2:2021, and is an index that indicates the degree of peakedness of the height distribution from the mean plane. When Sku is 3, the surface shape is symmetrical (normal distribution) with respect to the mean plane, when Sku exceeds 3, the height distribution has a peaked shape, and when Sku is less than 3, the height distribution tends to have a flattened shape.

[0086] In the present specification, the cutoff value for measuring Sku (kurtosis) is 0. In addition, in the present specification, Sku (kurtosis) is the average value of measurements taken at any 10 points.

[0087] (6) Matte layer material The matte layer contains at least a cured resin, and may further contain various additives described below.

[0088] (i) Cured resin The cured resin is a cured product of a curable resin composition. The resin contained in the curable resin composition is preferably an ionizing radiation curable resin, since it is easy to form a specific surface shape. In addition, an ionizing radiation curable resin is preferable in consideration of the ease with which a matte layer can be formed and the ease with which surface properties such as scratch resistance, strength, and weather resistance, as well as processability, can be improved.

[0089] The ionizing radiation-curable resin is a resin having an ionizing radiation-curable functional group, which is a group that crosslinks and cures upon irradiation with ionizing radiation. Examples of the ionizing radiation-curable functional group include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group.

[0090] The term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group, and the term "(meth)acrylate" refers to an acrylate or a methacrylate.

[0091] Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0092] Ionizing radiation curable resins include electron beam curable resins and ultraviolet curable resins. Among these, ultraviolet curable resins are preferred. They can reduce the internal haze of the matte layer. They can also stabilize wrinkle formation by a wrinkle formation stabilizer, thereby improving the matte effect stably.

[0093] Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0094] The polymerizable monomer is preferably a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule, and particularly preferably a polyfunctional (meth)acrylate monomer. Examples of the polyfunctional (meth)acrylate monomer include a (meth)acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the ionizing radiation-curable functional group.

[0095] The number of functional groups of the polyfunctional (meth)acrylate monomer is, for example, 2 or more and 8 or less, and may be 2 or more and 6 or less. Furthermore, when the number of functional groups is within the above range, a wrinkled structure is easily obtained. These polyfunctional (meth)acrylates may be used alone or in combination of two or more types.

[0096] The polymerizable monomers can be used alone or in combination of two or more, and it is preferable to use two or more polymerizable monomers in combination, which makes it easier to obtain a specific surface shape.

[0097] When two or more polymerizable monomers are used in combination, a combination of a monofunctional monomer and a polyfunctional monomer, or a combination of two or more polyfunctional monomers is preferred, and a combination of a polyfunctional monomer and a polyfunctional monomer is more preferred.

[0098] When a polyfunctional monomer is used, the number of functional groups is preferably 2 or more. The number of functional groups may be 8 or less, 6 or less, or 4 or less.

[0099] When a monofunctional monomer and a polyfunctional monomer are used in combination, the number of functional groups in the polyfunctional monomer is preferably 3 or less. In this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers.

[0100] When two or more types of polyfunctional monomers are used, it is preferable to combine a monomer having two functional groups with a monomer having three functional groups. In this case, the polyfunctional monomer is preferably a (meth)acrylate monomer.

[0101] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the ionizing radiation-curable functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.

[0102] Further examples of polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecule, such as novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0103] Examples of the polymerizable oligomer include 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, with urethane (meth)acrylate oligomer and polycarbonate (meth)acrylate oligomer being preferred, and urethane (meth)acrylate oligomer being more preferred.

[0104] The polymerizable oligomers can be used alone or in combination of two or more kinds, and it is preferable to use one kind of polymerizable oligomer alone.

[0105] The number of functional groups in the polymerizable oligomer is, for example, 2 or more and 8 or less, or may be 2 or more and 6 or less, or may be 2 or more and 4 or less.

[0106] The weight average molecular weight of the polymerizable oligomer is, for example, 2,500 or more and 7,500 or less, alternatively 3,000 or more and 7,000 or less, or 3,500 or more and 6,000 or less.

[0107] Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0108] In the present disclosure, it is preferable to use a combination of a polymerizable oligomer and a polymerizable monomer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane (meth)acrylate oligomer, more preferably a polyfunctional urethane acrylate oligomer. Furthermore, the polymerizable monomer is preferably a polyfunctional polymerizable monomer, more preferably a polyfunctional (meth)acrylate monomer, and even more preferably a polyfunctional acrylate monomer. It can stabilize wrinkle formation, stably improve the matte effect, reduce the internal haze of the matte layer, and further improve surface properties such as processing properties, scratch resistance, and weather resistance.

[0109] When a polymerizable oligomer and a polymerizable monomer are used in combination, the content of the polymerizable oligomer relative to 100 parts by mass of the total of the polymerizable oligomer and the polymerizable monomer is, for example, 20 parts by mass or more, or alternatively, 25 parts by mass or more, or 30 parts by mass or more, and the content of the polymerizable oligomer is, for example, 90 parts by mass or less, or alternatively, 80 parts by mass or less, or alternatively, 70 parts by mass or less.

[0110] Furthermore, polymerizable oligomers can be used in combination, and it is preferable to use a combination of two polymerizable oligomers with different numbers of functional groups. In this case, the content of the polymerizable oligomer with the larger number of functional groups relative to 100 parts by mass of the total amount of polymerizable oligomers is, for example, 50 parts by mass or more, or may be 55 parts by mass or more, or 60 parts by mass or more, or may be 65 parts by mass or more.

[0111] (ii) Wrinkle-forming stabilizers The matte layer in the present disclosure may or may not contain a wrinkle formation stabilizer. When the matte layer does not contain a wrinkle formation stabilizer, internal haze can be reliably reduced.

[0112] On the other hand, when the matte layer contains a wrinkle formation stabilizer, wrinkles can be stably formed on the surface of the matte layer. Although a wrinkle structure can be formed in the matte layer without using a wrinkle formation stabilizer, the use of a wrinkle formation stabilizer stabilizes the formed wrinkle structure, resulting in a stable matte effect and uniform surface condition due to the stable formation of wrinkles over the entire surface of the matte layer. In this case, in order to reduce internal haze, it is preferable to at least one of or both of making the refractive index difference between the resin in the matte layer and the wrinkle formation stabilizer approximately the same and increasing the sphericity of the wrinkle formation stabilizer.

[0113] "Wrinkle formation stabilization" means that the in-plane distribution (variance σ) of wrinkle shape and wrinkle geometric characteristic values ​​(length, width, and length-to-width ratio of individual protrusions) and wrinkle surface properties (Ra, RSm, Spc, etc.) converges when a wrinkle formation stabilizer is added compared to when no additive is added. This also results in the in-plane distribution (variance σ) of the 60° gloss value of the surface shape, which will be described later, converging. Wrinkle formation stabilizers are added not to diffuse light, suppress light reflection, or to matte the surface, but to stabilize the wrinkle structure.

[0114] Therefore, even if the so-called "matting agents" in the prior art and the "wrinkle formation stabilizers" in the present disclosure have the same or similar constituent substances and average particle diameters, they differ in the mechanisms (actions) of light reflection suppression and matting, the structures for achieving light reflection suppression and matting, and the relationship between the amount used and the degree of surface gloss (gloss value).

[0115] In the prior art, matting agents used for light reflection suppression and matting exhibit a matting effect by themselves due to the light diffusion effect resulting from their physical shape. Specifically, particles generally referred to as matting agents generally have a refractive index difference between the particles and the surrounding resin and air, and exhibit a matting effect due to the light diffusion effect caused by the reflection of light rays corresponding to the particle's contour shape and the refractive interface. Therefore, if a matting agent is used in a matting layer, the external light (incident light) will be diffused by the matting agent, resulting in a decrease in contrast.

[0116] On the other hand, the wrinkle formation stabilizer does not exhibit a matte effect through light diffusion caused by the reflection and refraction of light rays by the particles themselves, but rather stabilizes the formation of wrinkles on the surface of the matte layer due to the wrinkle formation stabilizer, and imparts a stable matte effect to the decorative sheet through the light diffusion effect at the refractive index difference interface between this surface and air. Therefore, the wrinkle formation stabilizer used in the present disclosure differs from matting agents that exhibit a matte effect by themselves in terms of the mechanisms (actions) of light reflection suppression and matte, and the structure for exhibiting light reflection suppression and matte, etc. (even if the constituent substances and average particle diameters of both are the same or similar).

[0117] Furthermore, the relationship between the content of a "wrinkle formation stabilizer" and a "matt agent" also differs in terms of the surface gloss value. When the same substance A is used as a wrinkle formation initiator AW (W: wrinkle), and a specific amount C is added to form wrinkles on the surface, the 60° gloss value G of the surface is 60° AW (C) is the 60° gloss value G of the surface when the same substance A is used simply as a matting agent AM and is contained in a specific amount C, but no wrinkles are formed on the surface. 60° AM (C) is clearly lower than (C). In other words, the following relationship holds: G 60° AW (C) <G 60° AM (C)

[0118] The wrinkle formation stabilizer is not a matting agent, and specifically, any agent having an average particle size of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, can be used without any particular restrictions.

[0119] Here, the average particle size of particles such as wrinkle formation stabilizers refers to the average particle size (arithmetic mean diameter) measured for 100 randomly selected non-aggregated particles when a cross section of a matte layer is observed using a scanning electron microscope (SEM) at an accelerating voltage of 3.0 kV and a magnification of 50,000. The particle size is the value measured by sandwiching the cross section of the particle between two arbitrary parallel lines and measuring the distance between the two lines that is the longest.

[0120] As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of 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, polyester-based resin, and urethane-based resin. Organic particles are preferred to reduce the refractive index difference between the resin and the wrinkle formation stabilizer and the internal haze of the matte layer. Examples of inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, and zirconia. Among these, silica, which has excellent transparency, is preferred. Inorganic particles are preferred to improve the strength of the matte layer.

[0121] The shape of the wrinkle formation stabilizer is not particularly limited, but examples thereof include spherical, polyhedral, scaly, and amorphous shapes. In order to reduce the internal haze of the matte layer, a spherical shape is preferred. This is because a spherical shape is thought to suppress the diffusion of reflected light by the wrinkle formation stabilizer, making it less likely that a decrease in contrast will occur.

[0122] In order to reduce the internal haze of the matte layer, the sphericity of the wrinkle formation stabilizer is, for example, 10% or less, or may be 8% or less, or may be 5% or less. The lower limit of the sphericity of the wrinkle formation stabilizer is not particularly limited, but may be, for example, 0.1% or more, or may be 0.5% or more, in view of availability.

[0123] Here, "sphericity" refers to the average deviation of the outer shape of 10 randomly selected particles from a perfect circle. Specifically, it refers to the ratio (%) of the maximum radial distance between the smallest circumscribing circle (minimum circumscribing circle) that touches the surface of each particle in an electron microscope photograph of each particle to the radius of the smallest circumscribing circle.

[0124] When silica is used as a wrinkle formation stabilizer, it is preferable that the specific surface area measured by the BET method using nitrogen adsorption is small, because this suppresses light diffusion. 2 / g or more 800m 2 / g or less, and 100m 2 / g or more 500m 2 / g or less.

[0125] Similarly, a low oil absorption is preferable because it suppresses light diffusion. The oil absorption is, for example, 700 ml / 100 g or less, and may be 600 ml / 100 g or less. Here, the oil absorption is determined by the method described in JIS K6217-4:2017 "Determination of oil absorption."

[0126] The surface of the wrinkle formation stabilizer may be coated with an organic compound to suppress light diffusion. For the purpose of achieving a matte effect and reducing the internal haze of the matte layer, it is preferable to use at least one of two types of wrinkle formation stabilizers distinguished by their average particle diameter, with the wrinkle formation stabilizer having an average particle diameter of the smaller of 100% or less of the matte layer thickness or 30 μm or less. Specifically, the two types of wrinkle formation stabilizers are a first wrinkle formation stabilizer having an average particle diameter of 1 μm or more and an upper limit of the smaller of 100% or less of the matte layer thickness or 30 μm or less, and a second wrinkle formation stabilizer having an average particle diameter of less than 1 μm. The use of at least one of the two types of wrinkle formation stabilizers stabilizes wrinkle formation and provides a stable and excellent matte effect.

[0127] The average particle size of the first wrinkle formation stabilizer is 1 μm or more, with an upper limit of either 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. To stably improve the matte effect and reduce the internal haze of the matte layer, the average particle size of the first wrinkle formation stabilizer is, for example, 1.3 μm or more, or may be 1.5 μm or more, or 1.8 μm or more. Furthermore, the average particle size of the first wrinkle formation stabilizer, relative to the thickness of the matte layer, may be, for example, 90% or less of the thickness of the matte layer, 80% or less of the thickness of the matte layer, or 70% or less of the thickness of the matte layer. Furthermore, the absolute value of the average particle size of the first wrinkle formation stabilizer is, for example, 20 μm or less, or may be 10 μm or less, 8 μm or less, or 7 μm or less. The average particle size of the first wrinkle formation stabilizer may be the smaller of any combination of the upper limit relative to the thickness of the matte layer and the upper limit of the absolute value. For example, the upper limit may be the smaller of 90% or less of the thickness of the matte layer or 20 μm or less, or the smaller of 90% or less of the thickness of the matte layer or 10 μm or less. The thickness of the matte layer will be described later.

[0128] The second wrinkle formation stabilizer has an average particle size of less than 1 μm. To stabilize wrinkle formation, stably improve the matte effect, and reduce the internal haze of the matte layer, the second wrinkle formation stabilizer has an average particle size of, for example, 1 nm or more, or even 3 nm or more, or even 5 nm or more. The second wrinkle formation stabilizer has an average particle size of, for example, 900 nm or less, or even 700 nm or less, or even 500 nm or less. An average particle size close to or less than the visible light range is preferred because it reduces the internal haze of the matte layer in response to visible light.

[0129] To stabilize wrinkle formation by the wrinkle formation stabilizer, stably improve the matte effect, and reduce the internal haze of the matte layer, the content of the wrinkle formation stabilizer (when a first wrinkle formation stabilizer and a second wrinkle formation stabilizer are used in combination, the total content of these) is, for example, 0.5 parts by mass or more, or may be 0.75 parts by mass or more, or 1.0 parts by mass or more, or 1.2 parts by mass or more, relative to 100 parts by mass of resin. Furthermore, the upper limit of the content of the wrinkle formation stabilizer is not particularly limited in order to improve the stable matte effect and reduce the internal haze of the matte layer, but, for example, to improve the coatability of the curable resin composition and efficiently improve the matte effect, the upper limit may be, for example, 25.0 parts by mass or less, or may be 15.0 parts by mass or less, 10.0 parts by mass or less, 7.5 parts by mass or less, or 6.0 parts by mass or less, relative to 100 parts by mass of resin.

[0130] When a first wrinkle formation stabilizer and a second wrinkle formation stabilizer are used in combination, the respective contents of the first wrinkle formation stabilizer and the second wrinkle formation stabilizer are not particularly limited as long as the total content is within the above-mentioned range. The content of the second wrinkle formation stabilizer is, for example, 0.1 parts by mass or more, or 0.5 parts by mass or more, or even 1.0 parts by mass or more, relative to 100 parts by mass of the resin. Furthermore, the content of the second wrinkle formation stabilizer is, for example, 10.0 parts by mass or less, or 7.5 parts by mass or less, or 5.0 parts by mass or less, or even 3.5 parts by mass or less, relative to 100 parts by mass of the resin. Furthermore, the blending ratio of the first wrinkle formation stabilizer and the second wrinkle formation stabilizer, when the total amount of these is 100 parts by mass, may be, for example, 0 parts by mass or more and 95 parts by mass or less, 10 parts by mass or more and 90 parts by mass or less, 20 parts by mass or more and 80 parts by mass or less, or 30 parts by mass or more and 70 parts by mass or less.

[0131] As described above, organic particles and inorganic particles can be used as wrinkle formation stabilizers, and these particle types themselves can also be said to include those conventionally used as matting agents. In order for a matting agent to exhibit a matting effect itself due to the light diffusion effect resulting from its physical shape, it must be used in large quantities. However, in the present disclosure, even at a small content as described above, i.e., even at a content less than the content required for the matting effect itself to be exhibited due to the light diffusion effect resulting from its physical shape, a matting effect far superior to that obtained by a matting agent can be obtained. Therefore, it can be said that the decorative sheet of the present disclosure, despite being substantially free of a matting agent, stably forms wrinkles on the surface, thereby stably obtaining a superior low gloss feeling compared to when a matting agent is used, and reducing the internal haze of the matte layer.

[0132] (iii) Photopolymerization initiators and photopolymerization accelerators When the curable resin composition contains an ultraviolet curable resin, the curable resin composition preferably contains at least one of a photopolymerization initiator and a photopolymerization accelerator.

[0133] Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like.

[0134] The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate. Examples of the photopolymerization accelerator include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0135] The content of the photopolymerization initiator is, for example, 0.1 parts by mass or more, or may be 0.3 parts by mass or more, or may be 0.5 parts by mass or more, relative to 100 parts by mass of the resin. The content of the photopolymerization initiator is, for example, 5 parts by mass or less, or may be 3 parts by mass or less, or may be 1.5 parts by mass or less, or may be 1.0 part by mass or less, relative to 100 parts by mass of the resin. When the content of the photopolymerization initiator is within the above range, the effect of using the photopolymerization initiator efficiently can be obtained. The content of the photopolymerization accelerator is the same as that of the photopolymerization initiator described above.

[0136] (iv) Weatherproofing agent The matte layer may contain weathering agents such as ultraviolet absorbers and light stabilizers. The addition of a weathering agent can impart weather resistance to the matte layer. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. Examples of light stabilizers include hindered amine-based light stabilizers such as piperidinyl sebacate-based light stabilizers. The ultraviolet absorbers or light stabilizers may also have a reactive functional group with an ethylenic double bond in the molecule, such as a (meth)acryloyl group, a vinyl group, or an allyl group. Weathering agents such as ultraviolet absorbers and light stabilizers can be used alone or in combination.

[0137] The content of the ultraviolet absorber is, for example, 0.1 parts by mass or more, 1.0 parts by mass or more, 2.0 parts by mass or more, or 3.0 parts by mass or more, relative to 100 parts by mass of the resin. Furthermore, the content of the ultraviolet absorber is, for example, 15.0 parts by mass or less, 12.0 parts by mass or less, 10.0 parts by mass or less, or 6.0 parts by mass or less, relative to 100 parts by mass of the resin. When the content of the ultraviolet absorber is within the above range, the effect of using the ultraviolet absorber efficiently can be obtained. Furthermore, the content of the light stabilizer is the same as that of the ultraviolet absorber described above.

[0138] (7) Matte layer The matte layer in the present disclosure has a surface shape including a wrinkled structure and embossed portions on the first surface opposite to the substrate layer, thereby providing a good matte effect and feel.

[0139] The 60° gloss value of the first surface of the matte layer is, for example, 10.0 or less, optionally 7.5 or less, optionally 5.0 or less, optionally 4.0 or less, or optionally 3.6 or less.

[0140] Here, the 60° gloss value of the first surface of the matte layer refers to the 60° specular gloss measured in accordance with JIS K5600-4-7:1999, and can be measured using, for example, a gloss meter. The 60° gloss value of the first surface of the matte layer is the average value of measurements taken at any 10 points.

[0141] The internal haze of the matte layer is, for example, 4.0% or less, and may be 3.6% or less. On the other hand, the lower limit of the internal haze of the matte layer is not particularly limited, but is preferably substantially 0% or more. Here, "substantially" means taking into consideration measurement error.

[0142] Here, the internal haze of the matte layer can be measured in accordance with JIS K7136:2000. When measuring the internal haze of the matte layer, for example, a transparent layer is placed on the first surface of the matte layer to fill in the unevenness and make it flat. This eliminates the influence of haze due to the surface shape. Furthermore, when measuring the internal haze of the matte layer, only the matte layer constituting the decorative sheet is prepared separately.

[0143] The thickness of the matte layer is not particularly limited as long as it can form a specific surface shape, but is, for example, 3 μm or more, 3.2 μm or more, or 3.4 μm or more, and may be, for example, 300 μm or less, 200 μm or less, 150 μm or less, or 100 μm or less.

[0144] Here, the thickness of the matte layer is determined by measuring the thickness at 20 points on an image of the cross section of the decorative sheet taken using a scanning electron microscope (SEM), and averaging the values ​​at the 20 points. The SEM acceleration voltage is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of the other layers.

[0145] The matte layer in the present disclosure may be disposed partially or entirely on the substrate layer described below, and is preferably disposed entirely on the substrate layer.

[0146] (8) Method for forming a matte layer Examples of methods for forming the matte layer include a wrinkle structure forming process in which a curable resin composition for the matte layer is applied to the surface opposite the substrate layer to form a coating layer, and the coating layer is cured by irradiating it with ionizing radiation to form a precursor layer having a wrinkle structure; and an embossed portion forming process in which an embossed portion is formed by embossing the surface of the precursor layer on the wrinkle structure side to obtain the matte layer.

[0147] (i) Wrinkle structure formation treatment The wrinkle structure forming process is a process in which a matte layer curable resin composition is applied to the surface opposite the substrate layer to form a coating layer, and the coating layer is cured by irradiation with ionizing radiation to form a precursor layer having a wrinkle structure. The ionizing radiation irradiation process in the wrinkle structure forming process involves (1) irradiation with light of a first wavelength of 100 nm or more and less than 200 nm, and (2) at least one of irradiation with electron beams and light of a second wavelength of 200 nm or more and 400 nm or less, performed in this order.

[0148] Examples of methods for applying the curable resin composition include known methods such as gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. The thickness of the coating layer is not particularly limited and is appropriately selected depending on the desired thickness of the matte layer. In addition, when the curable resin composition contains a solvent, it is preferable to dry the solvent after applying the curable resin composition.

[0149] The coating layer is cured by irradiation with ionizing radiation to form a precursor layer having a specific wrinkle structure. The irradiation treatment is preferably carried out by performing at least the following irradiation treatments (1) and (2) in this order. (1) Irradiation treatment with light of a first wavelength of 100 nm or more and less than 200 nm (2) At least one of electron beam irradiation and second wavelength light irradiation of 200 nm or more and 400 nm or less By carrying out the above irradiation treatments (1) and (2), a specific wrinkle structure is easily formed.

[0150] Although the details of the mechanism by which irradiation by at least the above irradiation treatments (1) and (2) makes it easier to obtain a specific wrinkle structure are unknown, it is presumed that the mechanism is as follows.

[0151] First, when the irradiation treatment with the low-wavelength (short-wavelength) ultraviolet light described above is performed, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the layers below, so only the surface portion of the coating layer begins to harden, and it is thought that the wrinkle structure is formed by the hardening shrinkage that occurs only on the surface. In this way, it is thought that the formation of the wrinkle structure occurs when the coating layer is hardened only in a certain thickness direction from the surface by irradiation with the low-wavelength (short-wavelength) ultraviolet light.

[0152] Subsequently, by performing at least one of the irradiation treatments (2) above, namely, the electron beam irradiation treatment and the irradiation treatment using long wavelength (long wavelength) ultraviolet light of 200 nm or more and 400 nm or less, it is possible to promote curing from the surface-near portion, where curing progresses slowly, to the deep portion away in the depth direction while maintaining the wrinkle structure formed on the surface of the coating layer.

[0153] Although the irradiation treatment (1) above can cure the coating layer throughout its entire thickness and become a precursor layer, the curing state is improved by further combining it with the irradiation treatment (2) above. As a result, a wrinkled structure appears on the surface of the matte layer, making it easier to obtain a specific surface shape. Furthermore, the curing state across the entire thickness and the improved curing state are thought to improve scratch resistance.

[0154] The first wavelength light having a wavelength of 100 nm or more and less than 200 nm used in the irradiation treatment (1) above is preferably "excimer light," which includes light in the ultraviolet wavelength range from excited dimers, i.e., excimers, formed by discharge of rare gases such as Ar, Kr, Xe, and Ne, halogenated rare gases such as F, Cl, I, and Br, or mixed gases. Examples of the wavelength of excimer light and the excimer used as the light source include light with a wavelength of 126 nm radiated from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), and 193 nm (ArF). While spontaneous emission light and highly coherent laser light due to stimulated emission can both be used as excimer light, spontaneous emission light is usually sufficient. Discharge lamps that emit these types of light (ultraviolet rays) are also called "excimer lamps."

[0155] Excimer light has a single wavelength peak and a narrower half-width wavelength than ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps or mercury lamps). The use of such excimer light makes it easier to create wrinkle structures.

[0156] For the same reasons as above, the wavelength of the first wavelength light is, for example, 120 nm or more, or may be 140 nm or more, 150 nm or more, or 155 nm or more. Furthermore, the wavelength of the first wavelength light is usually less than 200 nm, preferably 172 nm (Xe2). Thus, to facilitate the development of wrinkle structures, it is preferable to use light with a shorter wavelength, and among low-wavelength (short-wavelength) ultraviolet light (wavelength: 280 nm or less), low-wavelength (short-wavelength) ultraviolet light in the range of less than 200 nm is preferred.

[0157] The integrated light amount of the first wavelength light is, for example, 1 mJ / cm 2 is equal to or greater than 2 mJ / cm 2 It may be more than 5 mJ / cm 2 The upper limit of the cumulative light amount of the first wavelength light is not particularly limited. In order to reduce the number of lamps required for irradiating the first wavelength light and to take into consideration productivity such as improved production efficiency, the cumulative light amount of the first wavelength light may be set to, for example, 1,000 mJ / cm. 2 less than 300 mJ / cm 2 may be less than 100 mJ / cm 2 may be less than 10 mJ / cm 2 It may be the following:

[0158] The UV irradiance is, for example, 1 mW / cm 2 and above 5 mW / cm 2 It may be 10 mW / cm or more. 2 The ultraviolet irradiance may be, for example, 10 W / cm 2 less than 3W / cm 2 may be less than 1 W / cm 2 In particular, when productivity is taken into consideration, the ultraviolet irradiance may be 500 mW / cm or less. 2 Less than 300mW / cm is preferable. 2 Less than 150 mW / cm is more preferable. 2 The following is even more preferred:

[0159] Furthermore, the oxygen concentration during irradiation with the first wavelength light is preferably lower, for example, 1,000 ppm or less, or may be 750 ppm or less, 500 ppm or less, or 300 ppm or less.

[0160] In the wrinkle structure forming process, it is preferable to perform the above-mentioned (1) irradiation process using light of a first wavelength of 100 nm or more and less than 200 nm, followed by at least one of the above-mentioned (2) electron beam treatment and irradiation process using light of a second wavelength of 200 nm or more and 400 nm or less.

[0161] The irradiation conditions of the electron beam employed in the irradiation treatment (2) above are not particularly limited as long as the curable resin composition is cured. The acceleration voltage of the electron beam is, for example, 10 kV or more, and may be 30 kV or more, 50 kV or more, or 75 kV or more. The acceleration voltage of the electron beam is, for example, 300 kV or less, 250 kV or less, or 200 kV or less. When the acceleration voltage of the electron beam is within the above range, the cured product is likely to retain the shape of the wrinkle structure. In addition, scratch resistance is improved. For the same reasons as above, the irradiation dose of the electron beam is, for example, 5 kGy or more, 10 kGy or more, or 15 kGy or more. The irradiation dose of the electron beam is, for example, 150 kGy or less, 125 kGy or less, or 100 kGy or less.

[0162] The electron beam source is not particularly limited as long as it can achieve the above-mentioned irradiation conditions, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used.

[0163] The second wavelength light of 200 nm or more and 400 nm or less used in the irradiation treatment (2) above can be irradiated using an ultraviolet irradiation device using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp. Alternatively, excimer light of wavelengths of 200 nm or more and 400 nm or less, such as 222 nm (KrCl), 247 nm (KrF), or 308 nm (XeCl), may be used.

[0164] The wavelength of the second wavelength light employed in the irradiation treatment (2) above is, for example, 330 nm or more and 390 nm or less. When the wavelength of the second wavelength light is within the above range, the shape of the wrinkle structure is more likely to be maintained as is. Furthermore, scratch resistance is improved. For the same reasons as above, the output of the ultraviolet irradiation device may be, for example, 50 W / cm or more and 100 W / cm or more. Furthermore, the output of the ultraviolet irradiation device may be, for example, 300 W / cm or less and 200 W / cm or less. Furthermore, the irradiation speed may be, for example, 1 r / min or more and 3 r / min or more. Furthermore, the irradiation speed may be, for example, 50 r / min or less and 10 r / min or less.

[0165] Furthermore, before the irradiation treatments (1) and (2), an irradiation treatment for pre-curing (3) may be performed. By pre-curing the entire coating layer by the irradiation treatment for pre-curing (3), an appropriate viscosity is imparted to the curable resin composition. Therefore, sagging of the wrinkle structure formed by the irradiation treatment (1) above can be suppressed, and the wrinkle structure can be better maintained.

[0166] The ionizing radiation light used in the irradiation treatment for pre-curing in (3) above is, for example, light with a wavelength of more than 320 nm, may be light with a wavelength of more than 320 nm but not more than 400 nm, or may be light with a wavelength of 385 nm or more but not more than 400 nm. By using light with such wavelengths (ultraviolet light) in the irradiation treatment in (3) above, the entire coating layer can be pre-cured efficiently.

[0167] The ultraviolet irradiance in the irradiation treatment (3) above is, for example, 0.01 W / cm 2 or more, and 0.1 W / cm 2 It may be 0.3 W / cm or more. 2 The ultraviolet irradiance may be, for example, 5 W / cm 2 less than 3W / cm 2 may be less than 2 W / cm 2 When the ultraviolet irradiance is within the above range, the coating layer is not completely cured, and the entire coating layer can be efficiently pre-cured.

[0168] The wavelength light used in the irradiation treatment (3) above can be irradiated using an ultraviolet irradiation device that uses, for example, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, or an LED light as a light source.

[0169] (ii) Embossed part formation process The embossed portion forming process is a process in which an embossed portion is formed on the wrinkled structure side of the precursor layer by embossing to obtain a matte layer. In the embossing process, for example, a sheet having a wrinkled structure (a precursor sheet of the decorative sheet) is heated and softened on a heated drum, then further heated with an infrared radiant heater, and pressed and shaped with an embossing plate with a desired concave-convex pattern, and then cooled and fixed. The heating temperature of the decorative sheet during the embossing process is, for example, from 80°C to 260°C, and may be from 100°C to 200°C.

[0170] 2.Base material layer The decorative sheet of the present disclosure has a substrate layer. The substrate layer is a member that supports the matte layer. Furthermore, by having the substrate layer, the decorative sheet has improved performance properties such as mechanical strength, suitability for post-processing, and design, thereby improving usability as a sheet.

[0171] The substrate layer is not particularly limited, and examples thereof include a resin substrate, a glass substrate, a metal substrate, and a fiber substrate. The type of substrate layer is appropriately selected depending on the application of the decorative sheet.

[0172] Resins used for the resin substrate include, for example, various synthetic resins and various natural resins. Examples of synthetic resins include thermoplastic resins and cured resins (cured products of curable resins). Considering the manufacturing suitability, handling suitability, and post-processing suitability of the decorative sheet, thermoplastic resins are preferred.

[0173] Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate, cellophane, and celluloid; styrene resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABS resins); polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins.

[0174] Examples of natural resins include natural rubber, pine resin, and amber, while examples of curable resins include ionizing radiation curable resins and thermosetting resins.

[0175] Examples of metals used for the metal substrate include aluminum or aluminum alloys such as duralumin, iron or iron alloys such as carbon steel and stainless steel, copper or copper alloys such as brass and bronze, gold, silver, chromium, nickel, cobalt, tin, and titanium. The metal substrate may have a plated film or an anodized film on its surface.

[0176] Examples of fibrous materials used for the fiber substrate include tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, parchment paper, glassine paper, wallpaper backing paper, paperboard, and plasterboard base paper; and woven or nonwoven fabrics made from fibers such as polyester resin fibers, acrylic resin fibers, protein- or cellulose-based natural fibers such as silk, cotton, and hemp, glass fibers, and carbon fibers. Various resins, such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin, may be added to the fiber substrate. When the fiber substrate is a paper substrate, the strength between the fibers of the paper substrate or the interlayer strength between the paper substrate and other substrates can be improved. Furthermore, fluffing can be suppressed. Resin addition methods include impregnation with the resin after papermaking, or incorporation of the resin during papermaking. Examples of paper substrates to which resin has been added include inter-fiber reinforced paper and resin-impregnated paper.

[0177] In the case of a fiber substrate, a permeation-preventing resin layer is preferably disposed on the matte layer side of the fiber substrate. Examples of resins used for the permeation-preventing resin layer include two-component curing urethane resins. The permeation-preventing resin layer can be formed by a method such as coating.

[0178] The substrate layer may contain additives as needed. In the case of a resin substrate, examples of additives include inorganic fillers, flame retardants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, light stabilizers, and colorants. Various additives can be used alone or in combination. The content of the additives is not particularly limited as long as it does not impair surface properties and processing properties, and can be appropriately set depending on the required properties.

[0179] In order to improve weather resistance, among the above additives, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers. The ultraviolet absorbers and light stabilizers may be the same as those used in the matte layer.

[0180] The substrate layer may be a single layer or a laminate of two or more layers. In the case of a laminate, the substrate layer may have two or more layers of the same type of substrate, or may have two or more layers of different types of substrate. In the present disclosure, the substrate layer can also serve as a decorative layer, which will be described later. Furthermore, the substrate layer may be transparent or opaque. When the substrate layer is opaque, the substrate layer can serve as a decorative layer.

[0181] The substrate layer may be colored. When the substrate layer is colored, the substrate layer can serve as a decorative layer. The coloring mode is not particularly limited, and may be transparent or opaque (hiding), which can be selected arbitrarily.

[0182] If the base layer is colored, it may contain a colorant. Examples of colorants include inorganic pigments such as white pigments (e.g., titanium white), iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo-based black pigments, and perylene-based black pigments; metal pigments consisting of scaly foil flakes such as aluminum and brass; and pearlescent pigments consisting of scaly foil flakes such as titanium dioxide-coated mica and basic lead carbonate. For example, if the surface hue of the adherend on which the decorative sheet is laminated varies and it is desired to conceal the surface hue and improve the color stability of the decorative layer, an inorganic pigment such as a white pigment may be used.

[0183] The substrate layer may be surface-treated to enhance adhesion with adjacent layers, such as a decorative layer or an adhesive layer. Examples of surface treatments include physical and chemical surface treatments, such as oxidation and roughening. Examples of oxidation methods include corona discharge treatment, chromium oxidation, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of roughening methods include sandblasting and solvent treatment. While these surface treatments are appropriately selected depending on the type of substrate layer, corona discharge treatment is generally preferred in terms of the effectiveness and ease of use of the surface treatment.

[0184] When the substrate layer is a laminate, an adhesive layer or a primer layer may be disposed between adjacent layers in order to improve the adhesion between the layers.

[0185] The thickness of the substrate layer is not particularly limited and is appropriately selected depending on the material of the substrate layer. In the case of a substrate layer containing a resin, the thickness of the substrate layer is, for example, 10 μm to 500 μm, or may be 20 μm to 300 μm, or may be 40 μm to 200 μm. In addition, when the substrate layer is a paper substrate, the basis weight is, for example, 20 g / m 2 More than 150g / m 2 less than 30 g / m 2 More than 100g / m 2 It may be the following:

[0186] 3.Decorative layer The decorative sheet of the present disclosure may have a decorative layer between the substrate layer and the matte layer. The decorative layer can impart a design to the decorative sheet. Furthermore, when the decorative sheet has a transparent resin layer as described below, the decorative layer may be disposed between the substrate layer and the transparent resin layer.

[0187] The decorative layer may be a colored layer, a patterned layer, or a metal layer. The decorative layer may also have a colored layer and a patterned layer. The colored layer may be a so-called solid colored layer disposed over the entire surface of the decorative sheet. The colored layer preferably contains a binder resin and a colorant. The colored layer can be formed by a coating method.

[0188] The pattern (design) of the pattern layer is not particularly limited, and examples include wood grain patterns such as tree rings and vessels on the surface of a wooden board; stone grain patterns on the surface of stone slabs such as marble and granite; fabric grain patterns on the surface of fabric; leather grain patterns on the surface of leather; geometric patterns; letters; figures; and combinations thereof.

[0189] The design layer contains, for example, a binder resin and a colorant. The design layer can be formed by a printing method. The binder resin used in the coloring layer and the design layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. Various resins can also be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

[0190] Examples of colorants used in the colored layer and the pattern layer include pigments and dyes. Among these, the colorant is preferably a pigment with excellent hiding power and weather resistance. The pigment may be the same as the pigment used in the base layer. The content of the colorant is, for example, 5 to 90 parts by mass, 15 to 80 parts by mass, or 30 to 70 parts by mass, per 100 parts by mass of the binder resin.

[0191] The colored layer and the design layer may contain additives such as ultraviolet absorbers, weathering agents such as light stabilizers, extender pigments, stabilizers, plasticizers, hardeners, and catalysts, as required.

[0192] Examples of metal materials used for the metal layer include aluminum, chromium, tin, indium, and titanium. The metal layer can be formed by vapor deposition.

[0193] The thickness of the decorative layer is appropriately selected depending on the desired design and type of decorative layer. When the decorative layer has at least one of a colored layer and a patterned layer, the thickness of the decorative layer is, for example, 0.5 μm to 20 μm, or alternatively, 1 μm to 10 μm, or alternatively, 2 μm to 5 μm, in consideration of concealing the base color of the adherend and improving the design.

[0194] 4. Other layers As shown in FIG. 1, the decorative sheet of the present disclosure has a substrate layer 1 and a matte layer 2. Alternatively, as shown in FIG. 2, the decorative sheet 10 may have a substrate layer 1, a decorative layer 3, and a matte layer 2. Meanwhile, the decorative sheet of the present disclosure may further have other layers. Examples of such other layers include a transparent resin layer, an adhesive layer, a separator layer, and a primer layer. For example, the decorative sheet 10 shown in FIG. 5 has, in addition to the substrate layer 1, the decorative layer 3, and the matte layer 2, a transparent resin layer 6, an adhesive layer 7, and a separator layer 8.

[0195] (1)Transparent resin layer The decorative sheet of the present disclosure may have a transparent resin layer between the matte layer and the decorative layer, which can increase the strength of the decorative sheet.

[0196] The transparent resin layer may be transparent enough to allow the decorative layer to be seen, and may be colorless and transparent, colored and transparent, or translucent.

[0197] Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, ABS resins, acrylic resins, and vinyl chloride resins. In consideration of processability, polyolefin resins and vinyl chloride resins are preferred. The resins may be used alone or in combination of two or more.

[0198] The transparent resin layer may contain additives as needed. Examples of the additives include weather-resistant agents such as ultraviolet absorbers and light stabilizers. The weather-resistant agents may be appropriately selected from those described above.

[0199] In consideration of processability, the thickness of the transparent resin layer is, for example, 20 μm or more and 150 μm or less, or may be 40 μm or more and 120 μm or less, or may be 60 μm or more and 100 μm or less.

[0200] Examples of methods for forming the transparent resin layer include a method of applying a resin composition and a method of laminating a resin film by dry lamination.

[0201] (2) Adhesive layer The decorative sheet of the present disclosure may have an adhesive layer on the side of the substrate layer opposite the matte layer. In this case, the adhesive layer is, for example, a member for attaching the decorative sheet to an adherend. Furthermore, when the decorative sheet has a transparent resin layer, the adhesive layer may be disposed between the transparent resin layer and the decorative layer.

[0202] The adhesive layer may be transparent or opaque.

[0203] Examples of adhesives used in the adhesive layer include curing adhesives and pressure-sensitive adhesives. Specific examples include urethane adhesives, acrylic adhesives, epoxy adhesives, silicone adhesives, and rubber adhesives. Optically clear adhesive (OCA) or optically clear resin (OCR) can also be used for the adhesive layer.

[0204] From the viewpoint of efficiently obtaining a desired adhesive strength, the thickness of the adhesive layer is, for example, 0.5 μm or more and 50 μm or less, or may be 0.7 μm or more and 30 μm or less, or may be 1.0 μm or more and 20 μm or less.

[0205] Examples of methods for forming the adhesive layer include a method of applying an adhesive composition and a method of laminating an adhesive film by dry lamination.

[0206] (3) Separator layer The decorative sheet of the present disclosure may have a separator layer on the side of the adhesive layer opposite the substrate layer. The separator layer is a member that protects the adhesive layer and is peeled off when the decorative sheet is attached to an adherend. Conventionally known separator layers can be used.

[0207] (4) Primer layer The decorative sheet of the present disclosure may have a primer layer to improve interlayer adhesion between the multiple layers that make up the decorative sheet. The primer layer may be disposed between any layer between the matte layer and the substrate layer. Furthermore, if the decorative sheet has a transparent resin layer, the primer layer may be disposed between the transparent resin layer and the matte layer. Furthermore, the primer layer may be disposed on the side of the substrate layer opposite the decorative layer (rear primer layer).

[0208] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.

[0209] Examples of binder resins include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin (nitrocellulose), and cellulose acetate resin. These can be used alone or in combination.

[0210] The binder resin may be a resin obtained by crosslinking and curing the above-mentioned resin with the addition of a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent. For example, a resin obtained by crosslinking and curing a polyol-based resin such as an acrylic polyol resin with an isocyanate-based curing agent is preferred, and a resin obtained by crosslinking and curing an acrylic polyol resin with an isocyanate-based curing agent is more preferred.

[0211] The thickness of the primer layer is, for example, 0.5 μm or more, or may be 1 μm or more, or 2 μm or more, and the thickness of the primer layer is, for example, 10 μm or less, or may be 8 μm or less, or may be 6 μm or less.

[0212] The primer layer can be formed by applying a resin composition, and then drying and curing it as necessary.

[0213] B. Manufacturing method of decorative sheet 6 is a flow chart illustrating a method for manufacturing a decorative sheet according to the present disclosure. As shown in FIG. 6(a), a matte layer is formed on one side of a substrate layer (matte layer forming step). The matte layer forming step further includes a process of applying a curable resin composition for the matte layer to one side of the substrate layer to form a coating layer, and curing the coating layer by irradiating it with ionizing radiation to form a precursor layer having a wrinkled structure (wrinkle structure forming process), and a process of embossing the surface of the precursor layer on the wrinkled structure side to form an embossed portion to obtain a matte layer (embossed portion forming process).

[0214] The ionizing radiation irradiation process in the wrinkle structure formation process involves (1) irradiation with light of a first wavelength of 100 nm or more but less than 200 nm, and (2) irradiation with at least one of electron beam irradiation and light of a second wavelength of 200 nm or more but less than 400 nm, in this order. In this disclosure, the conditions for each process are adjusted so that the Rz and 45° reflection intensity of the first surface are within a predetermined range. As shown in FIG. 6(b), a decorative layer may be formed before the matte layer formation process (decorative layer formation process).

[0215] According to the present disclosure, by carrying out the above-described steps, a decorative sheet can be obtained that has good matte properties, good tactile feel, low glare, and good design visibility.

[0216] 1.Matte layer formation process The matte layer forming step is a step of forming a matte layer on one side of the base layer. The matte layer forming step further includes a wrinkle structure forming process and an embossed portion forming process. The wrinkle structure forming process and the embossed portion forming process are the same as those described in "A. Decorative Sheet."

[0217] 2.Decorative layer formation process The method for producing a decorative sheet according to the present disclosure may include a decorative layer forming step of forming a decorative layer on one side of the substrate layer prior to the matte layer forming step. If the decorative layer forming step is performed, a matte layer is formed on the surface of the decorative layer opposite the substrate layer, either directly or via another layer, in the subsequent matte layer forming step.

[0218] The decorative layer forming step is a step of forming a decorative layer on one side of the base layer. For example, a method of forming the decorative layer includes a coating method using a decorative layer forming ink containing a colorant, a binder resin, and a solvent (or a dispersion medium). For example, the decorative layer is obtained by coating the decorative layer forming ink on one side of the base layer and drying it.

[0219] Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water.

[0220] Examples of the coating method include printing. Examples of printing methods include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Examples of coating methods for forming a solid layer include various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating.

[0221] 3. Decorative sheet The decorative sheet obtained by each of the above steps is the same as that described in "A. Decorative sheet."

[0222] C. Decorative materials 7 is a schematic cross-sectional view illustrating a decorative material according to the present disclosure. In the decorative material 100 shown in FIG. 7, the adherend 20 and the decorative sheet 10 are T 7, the decorative sheet 10 and the adherend 20 are bonded together via an adhesive layer 7 of the decorative sheet 10. In addition, the matte layer 2 is disposed on the opposite side of the substrate layer 1 from the adherend 20. In FIG.

[0223] According to the present disclosure, by using the decorative sheet described above, a decorative material can be obtained that has good matte properties, good feel, low glare, and good design visibility.

[0224] 1.Adherent The shape of the adherend is not particularly limited, and examples thereof include plate-like shapes such as flat plates and curved plates; three-dimensional shapes such as cylinders and polygonal pillars; and sheets. The adherend may be a wooden member. Examples of the wooden member include wood fiberboards. Examples of the wood fiberboard include wood veneers, wood plywood, laminated lumber, particle board, and MDF (medium density fiberboard). Examples of the material for the wooden member include wood such as cedar, cypress, pine, and lauan.

[0225] The adherend may be a metal member. Examples of metals used for the metal member include iron, aluminum, copper, and alloys containing one or more of these metals. The adherend may also be a ceramic member such as glass or porcelain, or a non-ceramic member such as gypsum, cement, ALC (aerated lightweight concrete), or calcium silicate.

[0226] The adherend may be a resin member. Examples of resins used for the resin member include acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS resin, phenol resin, vinyl chloride resin, cellulose resin, and rubber.

[0227] 2. Decorative sheet The decorative sheet in this disclosure is the same as that described above in "A. Decorative Sheet," and therefore will not be described here.

[0228] 3. Cosmetic materials The uses of the decorative material in the present disclosure are not particularly limited, and examples thereof include architectural components such as walls, ceilings, floors, roofs, eaves ceilings, fences, and gates; fittings or fixtures such as window frames, doors, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various types of furniture used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets and other appliances and office equipment; and interior or exterior components for vehicles. Furthermore, the decorative material in the present disclosure is preferably a floor component or a wall component. Furthermore, the decorative material in the present disclosure may be a component used outdoors (exterior component) or a component used indoors (interior component).

[0229] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure. [Example]

[0230] [Example 1] (Preparation of Curable Resin Composition for Matte Layer) A mixture was obtained by mixing 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer). The mixture was then added with a wrinkle formation stabilizer (silica particles, average particle size: 3 μm, specific surface area: 100 m). 2 3 parts by mass of a benzophenone-based photopolymerization initiator was added to the mixture, and a curable resin composition for the matte layer was obtained.

[0231] (Production of decorative sheets) A decorative layer (a dark wood grain pattern layer) was formed on a base layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied to the decorative layer to form a primer layer with a thickness of 2 μm. A curable resin composition for a matte layer was applied to the primer layer in a dry coating amount of 15 g / m. 2 The coating layer was then irradiated with ultraviolet light using a UV irradiation device comprising LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm). 2 , cumulative light intensity 30~100mJ / cm 2 ), and preliminary curing was performed. Next, ultraviolet light was irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe2), ultraviolet output density 30 mW / cm 2 , cumulative light intensity 5~100mJ / cm 2 , nitrogen atmosphere). Further, an electron beam was irradiated (accelerating voltage 100 to 150 kV, irradiation dose 30 to 100 kGy) to form a precursor layer having a wrinkled structure.

[0232] The sheet with the precursor layer formed thereon was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate A) was pressed against the surface of the precursor layer (the surface with the wrinkled structure formed thereon) to form a matte layer with a wrinkled structure and embossed portions, thereby obtaining a decorative sheet.

[0233] [Example 2] First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a dark wood grain patterned layer), a primer layer, and a precursor layer were formed on a substrate layer (polyolefin resin) in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate B) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0234] [Example 3] First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a light-colored wood grain patterned layer) was formed on a substrate layer (polyolefin resin). Next, a primer layer and a precursor layer were formed on the decorative layer in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate A) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0235] [Comparative Example 1] First, 15 parts by mass of a matting agent (silica particles, average particle size: 8 μm) was further added to the curable resin composition for the matte layer prepared in Example 1 to obtain a curable resin composition for the matte layer. Next, a decorative layer (a dark wood grain pattern layer) was formed on a substrate layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied on the decorative layer to form a primer layer with a thickness of 2 μm. The curable resin composition for the matte layer was applied on the primer layer in a dry application amount of 15 g / m. 2 The coating layer was irradiated with electron beams (acceleration voltage 100 to 150 kV, exposure dose 30 to 100 kGy) to form a decorative sheet having a matte layer.

[0236] Comparative Example 2 First, a curable resin composition for a matte layer was obtained in the same manner as in Comparative Example 1. Next, a decorative layer (a light-colored wood grain pattern layer) was formed on a base layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied on the decorative layer to form a primer layer with a thickness of 2 μm. The curable resin composition for a matte layer was applied on the primer layer in a dry application amount of 15 g / m. 2 The coating layer was irradiated with electron beams (acceleration voltage 100 to 150 kV, exposure dose 30 to 100 kGy) to form a decorative sheet having a matte layer.

[0237] Comparative Example 3 First, a curable resin composition for a matte layer was obtained in the same manner as in Comparative Example 1. Next, a decorative layer (a dark wood grain pattern layer) was formed on a base layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied to the decorative layer to form a primer layer having a thickness of 2 μm. The curable resin composition for a matte layer was applied to the primer layer in a dry coating amount of 15 g / m. 2 The coating was applied at a rate of 100-150 kV to form a coating layer. The coating layer was irradiated with an electron beam (acceleration voltage 100-150 kV, exposure dose 30-100 kGy) to form a precursor layer. The sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate A) was pressed against the surface of the precursor layer to form a matte layer with embossed portions. This resulted in a decorative sheet.

[0238] Comparative Example 4 First, a curable resin composition for a matte layer was obtained in the same manner as in Comparative Example 1. Next, a decorative layer (a dark wood grain pattern layer) was formed on a base layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied to the decorative layer to form a primer layer having a thickness of 2 μm. The curable resin composition for a matte layer was applied to the primer layer in a dry coating amount of 15 g / m. 2The coating was applied at a rate of 100-150 kV to form a coating layer. The coating layer was irradiated with an electron beam (acceleration voltage 100-150 kV, exposure dose 30-100 kGy) to form a precursor layer. The sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate C) was pressed against the surface of the precursor layer to form a matte layer with embossed portions. This resulted in a decorative sheet.

[0239] Comparative Example 5 First, a curable resin composition for a matte layer was obtained in the same manner as in Comparative Example 1. Next, a decorative layer (a dark wood grain pattern layer) was formed on a base layer (polyolefin resin). Next, a composition containing an acrylic resin and a urethane resin was applied to the decorative layer to form a primer layer having a thickness of 2 μm. The curable resin composition for a matte layer was applied to the primer layer in a dry coating amount of 15 g / m. 2 The coating was applied at a rate of 100-150 kV to form a coating layer. The coating layer was irradiated with an electron beam (acceleration voltage 100-150 kV, exposure dose 30-100 kGy) to form a precursor layer. The sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate D) was pressed against the surface of the precursor layer to form a matte layer with embossed portions. This resulted in a decorative sheet.

[0240] Comparative Example 6 First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a dark wood grain pattern layer), a primer layer, and a precursor layer (matte layer) were formed on a base layer (polyolefin resin) in the same manner as in Example 1. Thereafter, a decorative sheet was prepared as it was without forming an embossed portion.

[0241] Comparative Example 7 First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a light-colored wood grain pattern layer) was formed on a substrate layer (polyolefin resin). Next, a primer layer and a precursor layer (matte layer) were formed on the decorative layer in the same manner as in Example 1. Thereafter, a decorative sheet was formed as it was without forming an embossed portion.

[0242] [Comparative Example 8] First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a dark wood grain patterned layer), a primer layer, and a precursor layer were formed on a substrate layer (polyolefin resin) in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate C) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0243] Comparative Example 9 First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a dark wood grain patterned layer), a primer layer, and a precursor layer were formed on a substrate layer (polyolefin resin) in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate D) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0244] [Comparative Example 10] First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (a light-colored wood grain patterned layer) was formed on a substrate layer (polyolefin resin). Next, a primer layer and a precursor layer were formed on the decorative layer in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate D) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0245] [Comparative Example 11] First, a curable resin composition for a matte layer was prepared in the same manner as in Example 1. Next, a decorative layer (black solid layer) was formed on a substrate layer (polyolefin resin). Next, a primer layer and a precursor layer were formed on the decorative layer in the same manner as in Example 1. Next, the sheet on which the precursor layer was formed was heated to 160°C, and an embossing plate for a wood grain pattern (embossing plate E) was pressed against the surface of the precursor layer (the surface on which the wrinkle structure was formed) to form a matte layer having a wrinkle structure and embossed portions. This resulted in a decorative sheet.

[0246] [Comparative Example 12] A mixture was obtained by mixing 30 parts by mass of a trifunctional urethane acrylate oligomer (trifunctional oligomer), 30 parts by mass of a trifunctional acrylate monomer (trifunctional monomer), and 40 parts by mass of a bifunctional acrylate monomer (bifunctional monomer). 0.8 parts by mass of a photopolymerization initiator (benzophenone-based) was added to the resulting mixture to obtain a curable resin composition for a matte layer. That is, the curable resin composition for a matte layer was prepared in the same manner as in Example 1, except that no wrinkle formation stabilizer was used. Next, in the same manner as in Example 1, a decorative layer (a dark wood grain pattern layer), a primer layer, and a precursor layer (matte layer) were formed on a substrate layer (polyolefin resin). Thereafter, a decorative sheet was produced as is without forming an embossed section.

[0247] [evaluation] (Maximum height Rz measurement) For the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12, the surface shape of the matte layer was measured and the maximum height Rz was calculated. When calculating Rz, the value corresponding to the cutoff value λc was set to 0. The laser microscope used was a shape analysis laser microscope ("VK-X150 (control unit) / VK-X160 (measurement unit)", manufactured by Keyence Corporation). The measurement conditions using the laser microscope were as follows. The measurement results are shown in Table 1. <Measurement conditions> ·Measurement direction: 2nd direction Objective lens: 10x Laser wavelength: 658nm Measurement mode: Surface profile mode Measurement pitch: 0.13 μm Measurement quality: High speed mode Analysis area: length: approximately 3,000 μm, width: approximately 10,000 μm

[0248] (Reflection intensity measurement using a goniophotometer) The reflection intensity of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12 was measured using a goniophotometer. Specifically, the reflection intensity at +45 degrees when visible light was incident on the matte layer of the decorative sheet at -45 degrees from the normal direction, and the maximum reflection intensity when visible light was incident on the matte layer at -75 degrees from the normal direction were measured using a goniophotometer. The goniophotometer used was a GP-200 goniophotometer manufactured by Murakami Color Research Laboratory Co., Ltd. The measurement conditions are shown below. <Measurement conditions> Light source: 12V, 50W halogen lamp Iris diaphragm: 10.5mm diameter Aperture: 9.1mm diameter ·Incidence angle: 45°, 75°

[0249] Specifically, the measurements were carried out according to the following procedure. (i) Sensitivity check A standard black glass plate BK-7 with a refractive index of 1.518 was attached. Two neutral density filters, one 1.0% and one 10.0%, were used. The sensitivity was set to 950. When the incident angle was 45°, the high-voltage adjustment knob was adjusted so that the display, which monitors the output signal, read 120. When the incident angle was 75°, the high-voltage adjustment knob was adjusted so that the display, which monitors the output signal, read 170.

[0250] (ii) Measurement of standard plates A standard black glass plate BK-7 with a refractive index of 1.518 was attached. Hereinafter, this will be referred to as the standard black glass plate. When measuring the standard black glass plate at an incident angle of 45°, only specularly reflected light near the receiving angle of 45° was detected. Therefore, the intensity of reflected light exiting the surface of the standard black glass plate at angles of 30.0° to 60.0° was measured in 0.1° increments. When measuring the standard black glass plate at an incident angle of 75°, only specularly reflected light near the receiving angle of 75° was detected. Therefore, the intensity of reflected light exiting the surface of the standard black glass plate at angles of 60.0° to 90.0° was measured in 0.1° increments. The intensity of reflected light from the standard black glass plate was measured before and after measuring the sample.

[0251] (iii) Preparation of the sample piece The decorative sheet was cut into a 5 cm x 5 cm square to prepare a test piece, which was then fixed to a suction sample stage.

[0252] (iv) Measurement of the sample The suction sample stage on which the test piece was fixed was fixed to the sample stage of the goniophotometer. The case where the sample was placed so that the first direction of the sample was parallel to the line connecting -90 degrees and +90 degrees with respect to the normal direction of one side of the decorative sheet was referred to as "fixed in the first direction." The case where the sample was placed so that the second direction of the sample was parallel to the line connecting -90 degrees and +90 degrees was referred to as "fixed in the second direction." Measurements were performed with the sample fixed in the first direction at an incident angle of 45°. Measurements were also performed with the sample fixed in the first direction and the second direction at an incident angle of 75°. Light from a light source was incident on the test piece, and the light reflected by the surface of the test piece was detected by a detector, and the intensity of the reflected light was measured. Hereinafter, the reflected light will also be referred to as reflected light. A neutral density filter attached to the light source side was selected so that the display, which monitors the output signal, would be approximately 20 to 180. Neutral density filters of 1.0%, 10.0%, and 50.0% were used alone or in combination. When measuring at an incident angle of 45°, the receiving angle was set to -90.0° to 90.0°, and when measuring at an incident angle of 75°, the receiving angle was set to 0.0° to 90.0°. By changing the detector angle, the intensity of the reflected light emitted from the surface of the test piece at the set receiving angle was measured in 0.1° increments.

[0253] (v) Analysis: Receiving angle The maximum intensity of reflected light from a standard black glass plate at an incident angle of 45° is A. MAX A MAX The light receiving angle at A was set to 45.0°, and the light receiving angle of the sample piece was corrected. MAX If the incident angle at 75° is 46.0°, the sample piece measurement angle is shifted by 1.0°. Specifically, the sample piece measurement angle of 46.0° is corrected to 45.0°, and the sample piece measurement angle of 47.0° is corrected to 46.0°. The maximum intensity of the reflected light from the black glass standard plate at an incident angle of 75° is C. MAX C MAX The light-receiving angle at the specimen was set to 75.0°, and the light-receiving angle of the specimen was corrected.

[0254] (vi) Analysis: Neutral Density Filter The intensity of the reflected light from the black glass standard plate and the sample piece was corrected for the use of a neutral density filter. For example, when a combination of 10.0% and 50.0% neutral density filters was used, the intensity of the reflected light was divided by 0.100, and then further divided by 0.500 to obtain the intensity of the reflected light after filter correction. MAX A MAX-S Then, the correction of the neutral density filter was performed. MAX C MAX-S In the measurement at an incident angle of 45°, the intensity of the reflected light from the sample piece after correction for the angle of reception and the neutral density filter was calculated as B. S In the measurement at an incident angle of 75°, the intensity of the reflected light from the sample piece after correction for the light receiving angle and the neutral density filter was calculated as D S It was decided.

[0255] (vii) Analysis: Standardization B at all light receiving angles when measuring at an incident angle of 45° S A MAX-S Divide by and multiply by 100 to get the normalized reflected light intensity B SS In measurements at an incident angle of 75°, D S C MAX-S Divide by and multiply by 100 to get the normalized reflected light intensity D SSIn FIG. 8, for Example 1, the horizontal axis shows the light receiving angle, and the vertical axis shows the normalized reflected light intensity B SS The graph shows the B of the incident angle of 45°. SS B 45-SS (45°reflection intensity). In the measurement of the incident angle of 75°, D when fixed in the first direction SS The maximum value of D SS1 When fixed in the second direction, D SS The maximum value of D SS2 D SS1 and D SS2 The absolute value of the difference D SSX D SS1 Divide by D SSX / D SS1 asked for.

[0256] (Embossed texture) Twenty evaluators evaluated the embossed feel of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12. Specifically, the matte layer of the decorative sheet was touched with the hand, and the feel was compared with a sample that did not have an embossed portion and had a wrinkled surface, and evaluated according to the following criteria. The results are shown in Table 1. <Evaluation criteria> ◎: 16 or more people rated the texture as being strongly uneven 〇: Between 11 and 15 people rated the texture as being strongly uneven ×: 10 or fewer people rated the texture as being strongly uneven

[0257] (embossed marks) Twenty evaluators evaluated the embossed marks on the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12. Specifically, the decorative sheets were attached to a plate and observed from multiple directions (first direction and second direction) from a distance of 50 cm, while freely changing the angle of the plate in each case, and evaluated according to the following criteria whether there was an angle at which the uneven shape resulting from the embossed portion was visible. <Evaluation criteria> 〇: 11 or more people rated that there was no angle from which the uneven shape could be seen ×: Fewer than 10 people evaluated that there was no angle at which the uneven shape could be seen

[0258] (Glare) Twenty evaluators evaluated the glare sensation of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12. Specifically, the decorative sheets were attached to a board, and while observing them from a distance of 50 cm from the second direction in which the glare sensation is most likely to be felt, the angle of the board was freely changed, and the angle at which the surface of the decorative sheet appeared to shine was evaluated according to the following criteria. The results are shown in Table 1. <Evaluation criteria> 〇: More than 11 people rated that there was no angle at which it looked shiny ×: Fewer than 10 people rated that there was no angle at which it looked shiny

[0259] (Glare uniformity) Twenty evaluators evaluated the uniformity of glare for the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 12. Specifically, the decorative sheets were attached to a board, and observed from multiple directions (first and second directions) at a distance of 50 cm while freely changing the angle of the board, and the degree of glare was evaluated according to the following criteria. The results are shown in Table 1. <Evaluation criteria> ◎: 16 or more people rated the glare as uniform and not noticeable Good: Between 11 and 15 people rated the glare as uniform and inconspicuous ×: 10 or fewer people evaluated that the degree of glare was uniform and not noticeable

[0260] [Table 1]

[0261] As shown in Table 1, Examples 1 to 3 were all evaluated as good in terms of feel, embossed marks, and glare. In contrast, Comparative Examples 1, 2, 6, 7, and 12 had low Rz, resulting in low evaluations of the embossed feel. Furthermore, Comparative Examples 4, 5, and 8 to 11 had high Rz, which made the embossed portions easily visible, resulting in low evaluations of the embossed marks. Furthermore, Comparative Examples 1 to 5 and 12 had high 45° reflection intensity, resulting in low evaluations of glare. Furthermore, Comparative Examples 8 to 11 were evaluated as good in terms of glare, but low in terms of uniformity of glare. In contrast, Examples 1 to 3 also received high evaluations of uniformity of glare.

[0262] Thus, the present disclosure provides, for example, the following inventions.

[0263] [1] A decorative sheet having a substrate layer and a matte layer, a first surface of the matte layer opposite to the base layer has a surface shape including a wrinkled structure and an embossed portion recessed toward the base layer in a thickness direction from a bottom of a recess of the wrinkled structure; When viewed from the thickness direction, the plurality of embossed portions extend in a first direction, In a second direction perpendicular to the first direction, the maximum height (Rz) of the first surface is 15 μm or more and 100 μm or less; A decorative sheet in which the 45° reflection intensity of said first surface in said first direction as measured by a goniophotometer is 0.50 or less.

[0264] [2] In the first direction, the 75° reflection intensity of the first surface measured by a goniophotometer is D SS1 In the second direction, the 75° reflection intensity of the first surface measured by a goniophotometer is defined as D SS2 And the above D SS1 and the above D SS2 The absolute value of the difference between SSX In this case, D SSX / D SS1 The decorative sheet according to [1], wherein the value of the surface roughness is 0.06 or less.

[0265] [3] The decorative sheet according to [1] or [2], wherein a decorative layer is disposed between the substrate layer and the matte layer.

[0266] [4] The decorative sheet according to any one of [1] to [3], wherein the 60° gloss value of the first surface is 10.0 or less.

[0267] [5] The decorative sheet according to any one of [1] to [4], wherein the wrinkle structure has an uneven shape caused by irregular wrinkles, and the irregular wrinkles have a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions.

[0268] [6] The decorative sheet according to any one of [3] to [5], wherein a transparent resin layer is disposed between the matte layer and the decorative layer.

[0269] [7] The decorative sheet according to any one of [1] to [6], wherein an adhesive layer is disposed on the surface of the substrate layer opposite the matte layer.

[0270] [8] A decorative sheet according to any one of [1] to [7], which is used for flooring components or building materials.

[0271] [9] A method for producing a decorative sheet according to any one of [1] to [8], a matte layer forming step of forming the matte layer on one surface side of the base material layer, The matte layer forming step includes: a wrinkle structure forming treatment in which a curable resin composition for a matte layer is applied to one surface side of the base layer to form a coating layer, and the coating layer is cured by an irradiation treatment with ionizing radiation, thereby forming a precursor layer having the wrinkle structure; an embossed portion forming process for forming the embossed portion on the wrinkle structure side of the precursor layer by embossing to obtain the matte layer, A method for manufacturing a decorative sheet, wherein the irradiation treatment with ionizing radiation in the wrinkle structure formation treatment is carried out in the order of (1) irradiation treatment with light of a first wavelength of 100 nm or more and less than 200 nm, and (2) at least one of irradiation treatments with electron beam irradiation and irradiation treatment with light of a second wavelength of 200 nm or more and 400 nm or less.

[0272]

[10] In the method for producing the decorative sheet, before the matte layer forming step, a decorative layer forming step of forming a decorative layer on one surface of the base material layer, The method for producing a decorative sheet according to [9], wherein in the matte layer forming step, the matte layer is formed on the side of the decorative layer opposite the substrate layer.

[0273]

[11] A decorative material having an adherend and a decorative sheet, The decorative material, wherein the decorative sheet is the decorative sheet according to any one of [1] to [8]. [Explanation of symbols]

[0274] 1...Base material layer 2...Matte layer 3...Decorative layer 4...Convex part 5...Recess 6…Transparent resin layer 7...Adhesive layer 8...Separator layer 10...Decorative sheet 100...Cosmetic materials

Claims

1. A decorative sheet having a substrate layer and a matte layer, a first surface of the matte layer opposite to the base layer has a surface shape including a wrinkled structure and an embossed portion recessed toward the base layer in a thickness direction from a bottom of a recess of the wrinkled structure; When viewed from the thickness direction, the plurality of embossed portions extend in a first direction, In a second direction perpendicular to the first direction, the maximum height (Rz) of the first surface is 15 μm or more and 100 μm or less; A decorative sheet in which the 45° reflection intensity of said first surface measured with a goniophotometer in said first direction is 0.50 or less.

2. In the first direction, the 75° reflection intensity of the first surface measured by a goniophotometer is D ＳＳ１ In the second direction, the 75° reflection intensity of the first surface measured by a goniophotometer is defined as D ＳＳ２ and the D ＳＳ１ and the above D ＳＳ２ The absolute value of the difference between ＳＳＸ In this case, D ＳＳＸ / D ＳＳ１ The decorative sheet according to claim 1, wherein is 0.06 or less.

3. The decorative sheet according to claim 1 , wherein a decorative layer is disposed between the substrate layer and the matte layer.

4. 2. The decorative sheet according to claim 1, wherein the 60° gloss value of said first surface is 10.0 or less.

5. 2. The decorative sheet according to claim 1, wherein the wrinkle structure has an uneven shape caused by irregular wrinkles, and the irregular wrinkles have a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions.

6. The decorative sheet according to claim 3 , wherein a transparent resin layer is disposed between the matte layer and the decorative layer.

7. The decorative sheet according to claim 1 , wherein an adhesive layer is disposed on the surface of said substrate layer opposite said matte layer.

8. The decorative sheet according to claim 1, which is used for flooring members or building materials.

9. A method for producing a decorative sheet according to any one of claims 1 to 8, a matte layer forming step of forming the matte layer on one surface side of the base material layer, The matte layer forming step includes: a wrinkle structure forming treatment in which a curable resin composition for a matte layer is applied to one surface side of the base layer to form a coating layer, and the coating layer is cured by an irradiation treatment with ionizing radiation, thereby forming a precursor layer having the wrinkle structure; an embossed portion forming process for forming the embossed portion on the wrinkle structure side of the precursor layer by embossing to obtain the matte layer, In the irradiation treatment with ionizing radiation in the wrinkle structure forming treatment, (1) an irradiation treatment with light of a first wavelength of 100 nm or more and less than 200 nm, and (2) at least one of an electron beam irradiation treatment and an irradiation treatment with light of a second wavelength of 200 nm or more and 400 nm or less are carried out in this order.

10. In the method for producing the decorative sheet, before the matte layer forming step, a decorative layer forming step of forming a decorative layer on one surface of the base material layer, The method for producing a decorative sheet according to claim 9 , wherein in the matte layer forming step, the matte layer is formed on the surface of the decorative layer opposite to the substrate layer.

11. A decorative material having an adherend and a decorative sheet, A decorative material, wherein the decorative sheet is the decorative sheet according to any one of claims 1 to 8.

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