Decorative sheets and decorative materials

Abstract

To provide a decorative sheet which has extremely excellent scratch resistance capable of preventing bored scratch and recessed scratch and gloss change and also has excellent dirt wipability, and a decorative material using the decorative sheet.SOLUTION: A decorative sheet has a surface protective coat layer and a base film layer, in which the surface protective coat layer has a recess on a surface opposite to a side formed with the base film layer, the base film layer includes at least a decorative layer, a first olefin resin layer and a primer layer, and the recess has a density when the surface of the decorative sheet is viewed of 15% or more, an average width of 200 μm or more, and a maximum depth of 15 μm or more and 90 μm or less.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a decorative sheet and a decorative material. [Background technology]

[0002] BACKGROUND ART Decorative materials are generally used when it is desired to decorate components used in building materials, furniture, home appliances, and the like. Usually, in a decorative material, a structure in which a pattern layer is simply provided directly on a substrate does not provide sufficient surface performance such as scratch resistance, stain resistance, and weather resistance, so surface performance is imparted by laminating a decorative sheet in which a transparent resin film is laminated onto the pattern layer provided on the substrate. In addition, the surface of such a decorative sheet is formed with irregularities to improve the wood grain design.

[0003] For example, Patent Document 1 discloses a decorative sheet to be laminated to a substrate, characterized in that the sheet has at least a first transparent resin layer, a design layer, a second transparent resin layer, and a transparent protective layer, in that order, and the transparent protective layer is composed of an ionizing radiation curable resin.

[0004] For example, Patent Document 2 discloses a decorative sheet having a first olefin resin layer, a second olefin resin layer, and a surface protective layer in this order, in which the indentation hardness HIT of the second olefin resin layer is <2> and the indentation hardness HIT of the surface protective layer <1> The decorative sheet is characterized in that the above and above satisfy a specific relationship.

[0005] In recent years, many decorative materials made by laminating a decorative sheet onto the surface of a wood substrate have been released, but there is a growing demand for further improvement in scratch resistance. Until now, the majority of scratches on decorative materials that have resulted in market complaints and complaints have been gouges or dents, and even in scratch tests (pencil hardness tests, etc.) that are conducted as substitute tests, scratches have been evaluated based on the presence or absence of "gouges or dents."

[0006] However, as the market demands higher quality, a phenomenon known as "gloss change," which was not previously considered a problem, is now being criticized as a flaw, leading to complaints, and there is a demand for the development of decorative materials that are less susceptible to "gloss change." The "change in gloss" described above is a phenomenon that occurs when the surface is dragged under load, and the surface becomes smooth even if no gouges or dents are formed, which changes the reflection state of light shining on the surface, resulting in a different appearance of gloss on the surface. Patent Documents 1 and 2 do not consider "change in gloss," and there is room for further improvement. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-74683 [Patent Document 2] International Publication No. 2018 / 159660 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention solves the above-mentioned problems, and aims to provide a decorative sheet that has extremely excellent scratch resistance, capable of preventing not only gouges and dents but also gloss changes, and also has excellent dirt wiping properties, and a decorative material made using said decorative sheet. [Means for solving the problem]

[0009] The inventors have conducted extensive research to solve the above-mentioned problems and have discovered that in a decorative sheet comprising one or more base film layers including a surface protective coating layer and a decorative layer, by forming a predetermined groove-shaped recess on the surface of the surface protective coating layer opposite the base film layer side, it is possible to prevent not only gouges and dents, but also gloss changes, and further to achieve excellent ease of wiping off dirt, which has led to the completion of the present invention.

[0010] That is, the present invention is a decorative sheet comprising a surface protective coating layer and a base film layer, wherein the surface protective coating layer has a recess on the surface opposite to the side on which the base film layer is formed, the base film layer includes at least a decorative layer, a first olefin resin layer and a primer layer, and the recess has a density of 15% or more when viewed from the surface of the decorative sheet, an average width of 200 μm or more and a maximum depth of 15 μm or more and 90 μm or less.

[0011] In the decorative sheet of the present invention, the density of the recesses is preferably 50% or less. Furthermore, it is preferable that the maximum depth of the recess is 80 μm or less. The base film layer preferably contains a thermoplastic resin. The decorative sheet of the present invention preferably has a total thickness of 200 μm or more. In the decorative sheet of the present invention, the surface protective coating layer preferably has an indentation hardness of 100 MPa or more and a thickness of 10 μm or more. The present invention also provides a decorative material characterized by comprising the decorative sheet of the present invention laminated on a substrate. [Effects of the Invention]

[0012] The present invention can provide a decorative sheet having extremely excellent scratch resistance that can prevent not only gouges and dents but also changes in gloss, and a decorative material made using the decorative sheet. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1(a) is a schematic cross-sectional view of the decorative sheet of the present invention, and FIG. 1(b) is a schematic plan view of the decorative sheet of the present invention. [Figure 2] FIG. 2(a) is a schematic cross-sectional view illustrating the total thickness of the decorative sheet of the present invention, and FIG. 2(b) is a schematic cross-sectional view illustrating the total thickness of a decorative sheet of the present invention according to another embodiment. [Figure 3] 1 is a cross-sectional view schematically showing a preferred example of the decorative material of the present invention. [Figure 4] FIG. 10 is a schematic diagram illustrating a measurement area of ​​a recess. [Figure 5] FIG. 10 is a schematic diagram illustrating a method for selecting a recessed portion. [Figure 6] 6(a) to 6(c) are diagrams illustrating a method for measuring indentation hardness. DETAILED DESCRIPTION OF THE INVENTION

[0014] The decorative sheet and decorative material of the present invention will now be described. In the following description, the lower and upper limits of numerical ranges expressed with "to" mean "greater than or equal to" (for example, if α to β, it means greater than or equal to α and less than or equal to β).

[0015] The decorative sheet of the present invention comprises one or more base film layers including a surface protective coating layer and a decorative layer. FIG. 1(a) is a schematic cross-sectional view of the decorative sheet of the present invention, and FIG. 1(b) is a schematic plan view of the decorative sheet of the present invention. As shown in FIG. 1( a ), the decorative sheet 10 of the present invention comprises a surface protective coating layer 1 and a base film layer 2 .

[0016] <Decorative sheet> As shown in Figures 1(a) and (b), the decorative sheet 10 of the present invention comprises a surface protective coating layer 1 and one or more base film layers 2 including a decorative layer, and the surface protective coating layer 1 has a groove-shaped recess a on the surface opposite to the side on which the base film layer 2 is formed.

[0017] (recess) A groove-like recess a is formed on the surface of the decorative sheet 10 of the present invention. The recess a needs to be present at least in the surface protective coating layer 1 of the decorative sheet 10, and the depth of the recess a may be such that it remains within the surface protective coating layer 1, or it may extend to the second olefin resin layer 5 described below, or it may appear as a convex on the layer below or on the back surface. From the viewpoint of obtaining an excellent texture (tactile feel), it is preferable that the material not only remains within the surface protective coating layer 1, but also extends to the second olefin resin layer 5 and the first olefin resin layer 3 described below.

[0018] The pattern of the recesses a may be, for example, a wood grain vessel groove, an uneven stone surface, a cloth surface texture, a matte finish, a sand grain, a hairline, a linear groove, etc. From the viewpoint of improving the design, it is preferable that the pattern of the recesses a is a pattern that is in harmony with the design of the decorative layer 4 described below. For example, if the decorative layer 4 has a wood grain pattern, selecting a wood grain duct groove as the pattern of the recesses and harmonizing the wood grain of the decorative layer 4 with the wood grain of the recesses will result in a decorative sheet that is more realistic, full of texture, and has a luxurious feel.

[0019] In the decorative sheet 10 of the present invention, the density of the recesses a is 15% or more when the decorative sheet is viewed from the surface. If the density is less than 15%, gloss change cannot be sufficiently prevented and scratch resistance becomes insufficient. The density of the recesses a is preferably 50% or less. If it exceeds 50%, gouges are more likely to occur, and scratch resistance may be reduced. The lower limit of the density of the recesses a is preferably 20%, more preferably 25%, and more preferably 45%. In this specification, the "density of recesses" is measured by the following method.

[0020] (density of recesses) (1) As shown in Figure 4, a decorative sheet of the present invention is cut into a size of 100 mm x 100 mm to prepare a sample 40, and 10 measurement areas 41 are arbitrarily selected on the surface of the sample 40. At this time, the measurement areas 41 are selected at equal intervals on the sample 40 to prevent bias. In measuring the density of recesses, the size of one measurement area 41 is set to 20 mm×15 mm. (2) In each selected measurement area 41, the density of recesses is measured by the following method. (2-1) Measurement environment Measurement equipment: Keyence VK-X1000 shape analysis laser microscope Analysis software: Adobe Photoshop (2-2) Measurement procedure (i) Place the sample 40 on the sample stage of the VK-X1000 and adjust the focus. (ii) One measurement area 41 is selected and the surface shape is measured. (iii) Waviness is removed from the measured surface shape. (iv) The height display of the measurement data from which the waviness has been removed is changed to black and white. (v) The resulting image is saved as a TIF image and imported into Adobe Photoshop, after which the image is cropped. Cropping is performed evenly around the original image so that the width and height are 90% of the original image before processing. (vi) A portion of the image after trimming that corresponds to the recess is selected, and the area (number of pixels) occupied by the recess in the image is measured. in particular, (a) Select the blackest cell in the image (K value: 100%). (b) Implement color gamut specification processing (select cells with colors close to the specified color). To specify only the recessed portion, the tolerance for color gamut specification (color difference judgment parameter) is adjusted. Ensure that most of the recessed areas are selected and that most of the flat (non-recessed) areas are not selected. (c) Measure the number of pixels in the area specified in (b). (vii) The density (%) of recesses in one measurement area 41 is calculated using the following formula.

number

[0021] In the decorative sheet 10 of the present invention, the recesses a have an average width of 200 μm or more. If the average width is less than 200 μm, the effect of sufficiently improving gloss change cannot be obtained. The preferred lower limit of the average width is 220 μm, the preferred upper limit is 1000 μm, and the more preferred lower limit is 250 μm. In this specification, the "average width of the recesses" is measured by the following method.

[0022] (average width of recess) (1) As shown in Figure 4, a decorative sheet of the present invention is cut into a size of 100 mm x 100 mm to prepare a sample 40, and 10 measurement areas 41 are arbitrarily selected on the surface of the sample 40. At this time, the measurement areas 41 are selected at equal intervals on the sample 40 to prevent bias. In measuring the average width of the recesses, the size of one measurement area 41 is set to 4 mm x 4 mm. (2) In each of the selected measurement areas 41, the average width of the recesses is measured by the following method. (2-1) Measurement environment Measurement equipment: Keyence VK-X1000 shape analysis laser microscope (2-2) Measurement procedure (i) Place the sample 40 on the sample stage of the VK-X1000 and adjust the focus. (ii) One measurement area 41 is selected and the surface shape is measured. (iii) Waviness is removed from the measured surface shape. (iv) From the image after removing the undulations, measure the width of the recess in measurement area 1. First, three recesses to be measured are selected based on the following criteria. (A) A recess. (B) Two or more recesses do not overlap each other. (C) The aspect ratio of the recess (length of the major axis / length of the minor axis) is 10 or more. The "length of the major axis" is the distance between the two largest points on the contour of the recess. The "minor axis length" is the maximum distance between two points perpendicular to the major axis on the contour of the recess. The length of the dashed line of the groove-like recess shown in Figure 5 is the "long axis length," and the length of the thin line is the "short axis length." Based on the above criteria, the recesses A-1, B-1, C-1, C-2, and D shown in Figure 5 can be selected because they satisfy all of the above criteria (A) to (C). Note that although the entire recess B-1 is not included in the measurement area, it can be selected because its maximum width is not near the edge of the measurement area. Although recess B-2 has an aspect ratio of 10 or more, it is not entirely included in the measurement region and its maximum width is near the edge of the selection region, so it can only be measured if there are no other recesses that can be selected. On the other hand, recesses B-3, E-1, and E-2 cannot be selected because their aspect ratios are less than 10, and recess F cannot be selected because two recesses overlap. In the recess selected above, select the location where the width is greatest and measure its length. At this time, the direction of the measured width is parallel to the short axis of the groove-like recess. After measuring the widths of the groove-like recesses at the selected three points, average them and use the average value as the width of the recess in measurement area 1. (v) The steps (i) to (iv) are carried out for all selected measurement areas 41 (10 points in total), and the obtained values ​​are averaged to calculate the "average width of recesses" in the decorative sheet of the present invention.

[0023] Furthermore, in the decorative sheet 10 of the present invention, the maximum depth of the recesses a is 15 μm or more and 90 μm or less. If the maximum depth exceeds 90 μm, the ability to wipe off dirt deteriorates. The maximum depth is preferably 80 μm or less, and more preferably 70 μm or less. If the maximum depth is less than 15 μm, gloss change cannot be prevented.The maximum depth is preferably 20 μm or more, more preferably 25 μm or more, and even more preferably 30 μm or more. In this specification, the "maximum depth of the recess" is measured by the following method. The same steps (i) to (iii) as for the "average width of recesses" above are carried out. (vi) Three groove-like depressions are selected to measure the depth using the same criteria as for the "average width of the depressions." (vii) The image data obtained in (iii) is subjected to smoothing (condition: ±8). (viii) Measure the maximum depth of the selected recesses. In this case, "maximum depth" refers to the maximum distance parallel to the thickness direction from the bottom of the recess to the flat surface of the surface. After measuring the maximum depths of the groove-like recesses at the selected three points, the largest of the three points is taken as the maximum depth of the groove-like recesses in one measurement area. (ix) The steps (i) to (viii) are carried out for all selected measurement areas 41 (a total of 10 points), and the maximum of the depths of the recesses obtained is defined as the "maximum depth of the recesses" of the decorative sheet of the present invention. Note that the average depth can also be calculated by averaging the values ​​obtained at the 10 points.

[0024] (total thickness) The decorative sheet 10 of the present invention preferably has a total thickness of 200 μm or more. If the total thickness of the decorative sheet 10 is less than 200 μm, dents may not be prevented. The total thickness of the decorative sheet 10 is more preferably 220 μm or more, even more preferably 240 μm or more, and most preferably 250 μm or more. The upper limit of the total thickness of the decorative sheet 10 is not particularly limited, but is preferably 500 μm or less, and more preferably 400 μm or less.

[0025] Here, the total thickness of the decorative sheet 10 will be explained. FIG. 2(a) is a schematic cross-sectional view of a decorative sheet of the present invention, and FIG. 2(b) is a schematic cross-sectional view of a decorative sheet of the present invention according to another embodiment. When the decorative sheet 10 of the present invention has recesses on only one surface, the length in the thickness direction from surface A to surface B is the "total thickness" of the decorative sheet 10, as shown in FIG. 2(a). On the other hand, even if the decorative sheet 10 of the present invention has a recess on one side and a protrusion B' on the other side, as shown in Figure 2(b), the length in the thickness direction from surface A to surface B, which is a smooth surface, is the "total thickness" of the decorative sheet 10. Next, each layer that constitutes the decorative sheet 10 will be described.

[0026] (Surface protection coating layer) The decorative sheet 10 of the present invention has a surface protective coating layer 1. The surface protective coating layer 1 preferably has an indentation hardness of 100 MPa or more. If the indentation hardness of the surface protective coating layer 1 is less than 100 MPa, it may not be possible to prevent gloss changes. The surface protective coating layer 1 more preferably has an indentation hardness of 160 MPa or more, and even more preferably 200 MPa or more. On the other hand, the surface protective coating layer 1 preferably has an indentation hardness of 300 MPa or less, and more preferably 290 MPa or less. If the indentation hardness of the surface protective coating layer 1 exceeds 300 MPa, it becomes brittle, which can prevent changes in gloss, but it may become more susceptible to scratches and cracks when handling the decorative sheet 10 or when embossing to impart a design.

[0027] In this specification, the "indentation hardness" of each layer is expressed as a nanoindentation hardness measured using a surface film physical property tester, Triboindenter (registered trademark) "TI-950" (manufactured by HYSITRON Corporation). The indentation hardness (HIT) of each layer was measured using a Tribo Indenter (registered trademark) "TI-950" as follows.

[0028] (1) Using the Berkovich indenter 31 shown in Figure 6(a), the Berkovich indenter 31 is pressed into the measurement sample 30 as shown in Figure 6(b) in the direction of the arrow 32, which indicates the load application direction, under the indentation conditions described below. From the triangular pyramid-shaped geometric shape formed on the surface, the "contact projected area (Ap) (mm ) corrected by the standard method of the instrument" is calculated. 2 The hardness is calculated by dividing the maximum test load (Fmax) by the Ap. That is, HIT=Fmax / Ap. (2) Here, the indentation conditions were as follows: at room temperature (laboratory ambient temperature), as shown in Figure 6(c), for the surface protective coating layer 1, a load of 0 to 100 μN was first applied for 10 seconds (i.e., 10 μN / s), then a load of 100 μN (Fmax) was held for 5 seconds, and finally the load was removed from 100 to 0 μN for 10 seconds. Furthermore, for the first olefin resin layer 3 described later, a load of 0 to 50 μN is first applied over 5 seconds (i.e., 10 μN / s), then the load of 50 μN (Fmax) is maintained for 5 seconds, and finally the load is removed from 50 to 0 μN over 10 seconds. Typically, the indentation amount (h) is about 100 to 150 nm, so the thickness of the layer to be measured in the indentation direction should be 1.0 μm or more (preferably 1.5 μm or more). Ap is 24.50 [hmax-ε(hmax-hr)] 2 (where ε is a correction factor due to the geometric shape of the indenter, and hr is the depth of the triangular pyramidal geometric shape remaining on the surface after unloading.) (3) When measuring hardness, the hardness of the cross section of the layer to be measured is measured to avoid the influence of the hardness of layers other than the layer that will be the measurement sample 30. That is, the decorative sheet is embedded in resin (a cold-setting type two-component epoxy resin) and left to harden at room temperature for 24 hours or more, and then the hardened embedded sample is mechanically polished to expose the cross section of the layer to be measured, and the hardness of the cross section of each layer is measured by pressing a Berkovich indenter 31 into the cross section of the layer to be measured (a position that avoids the fine particles if the layer contains fine particles such as filler). (4) For each layer, the indentation hardness is measured at 10 locations to ensure uniformity, and the average values ​​of the 10 locations are designated as the “indentation hardness of the surface protective coating layer 1” and the “indentation hardness of the first olefin resin layer 3,” respectively.

[0029] The surface protective coating layer 1 is preferably made of a cured product of a curable resin composition, from the viewpoint of improving the surface properties of the decorative sheet 10 of the present invention, such as contamination resistance, scratch resistance, and chemical resistance, and further satisfying the indentation hardness described above. Examples of the curable resin composition include resin compositions containing a curable resin such as a thermosetting resin, a two-component curing resin, or an ionizing radiation curable resin. From the viewpoint of obtaining better surface properties, resin compositions containing a two-component curing resin or an ionizing radiation curable resin as the curable resin are preferred.

[0030] Examples of the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curing polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea co-condensation resin, silicon resin, and polysiloxane resin.

[0031] The thermosetting resin may contain a curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator. For example, curing agents such as isocyanate and organic sulfonate may be added to unsaturated polyester resins and polyurethane resins, organic amines may be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutylnitrile may be added to unsaturated polyester resins.

[0032] The surface protective coating layer 1 can be formed from the thermosetting resin, for example, by applying a solution of the thermosetting resin by a coating method such as roll coating or gravure coating, followed by drying and curing.

[0033] The two-component curing resin is not particularly limited as long as it is a resin that is cured by a main component and a curing agent, and preferably includes a two-component curing urethane resin in which the main component is a polyol (polyhydric alcohol) and the curing agent is an isocyanate curing agent.

[0034] Preferred examples of the base agent include polyols such as polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, and 1,6-hexanediol; and polyols having a hydroxyl group as a functional group, such as acrylic polyol, polyester polyol, and polyether polyol. These may be used alone or in combination.

[0035] The isocyanate curing agent may be any of the conventionally known compounds, such as aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), and naphthalene diisocyanate; and polyisocyanates such as aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), and hydrogenated tolylene diisocyanate. Adducts or polymers of these various isocyanates, such as adducts of tolylene diisocyanate and tolylene diisocyanate trimers, may also be used.

[0036] The ionizing radiation-curable resin is a resin that is cured by irradiation with ionizing radiation, i.e., electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, such as ultraviolet (UV) rays or electron beams (EB), as well as electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams. Specifically, the ionizing radiation-curable resin can be appropriately selected from commonly used polymerizable monomers, polymerizable oligomers, and prepolymers.

[0037] As the polymerizable monomer, for example, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and among these, a polyfunctional (meth)acrylate monomer is preferred. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more ethylenically unsaturated bonds in the molecule, and preferred examples include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. These (meth)acrylate monomers can be used alone or in combination of two or more.

[0038] Preferred examples of the polymerizable oligomer include oligomers having a radically polymerizable unsaturated group in the molecule, such as (meth)acrylate oligomers such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. These polymerizable oligomers can be used alone or in combination of two or more.

[0039] The curable resin composition may contain, in addition to the curable resin, a dispersant, etc., which will be described later.

[0040] The curable resin composition may contain additives such as ultraviolet absorbers, ultraviolet screening agents, light stabilizers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy-imparting agents, coupling agents, plasticizers, antifoaming agents, fillers, antiblocking agents, lubricants, and solvents, within the scope of the present invention. Among these, it is preferable to contain weather resistance agents such as ultraviolet absorbers and light stabilizers in order to improve weather resistance.

[0041] Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, and acrylonitrile-based compounds, and examples of the light stabilizer include hindered amine-based, acrylate-based, oxamide-based, and cyanoacrylate-based compounds.

[0042] The surface protective coating layer 1 may contain a dispersant. Examples of the dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicone oils, waxes, and modified resins. In addition, the nanoshells described in International Publication No. 2018 / 159660 and the like can also be suitably used. These dispersants can be used alone or in combination of two or more.

[0043] The content of the dispersant is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.05 parts by mass or more and 15 parts by mass or less, even more preferably 0.1 parts by mass or more and 10 parts by mass or less, and particularly preferably 0.3 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the resin component forming the surface protective coating layer 1.

[0044] The surface protective coating layer 1 preferably further contains inorganic fine particles from the viewpoint of improving scratch resistance. Examples of the inorganic fine particles include silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass. Furthermore, by controlling the type and content of the inorganic fine particles, the indentation hardness of the surface protective coating layer 1 can also be adjusted.

[0045] The average particle size of the inorganic fine particles is not limited, but is preferably 20 μm or less, more preferably 1 μm or more and 20 μm or less, and even more preferably 2 μm or more and 15 μm or less. The average particle size of the inorganic fine particles is the 50% particle size (d50: median size) when the particles in a solution are measured by a dynamic light scattering method and the particle size distribution is expressed as a cumulative volume distribution. The 50% particle size can be measured, for example, using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

[0046] The content of the inorganic fine particles is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 25 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the resin component forming the surface protective coating layer 1.

[0047] The thickness of the surface protective coating layer 1 is preferably 10 μm or more and 30 μm or less. By making the thickness of the surface protective coating layer 1 10 μm or more and 30 μm or less, it is possible to effectively prevent gouges, dents, and changes in gloss, and further, it is possible to effectively prevent cracking of the decorative sheet 10 of the present invention, and it is also possible to improve handleability. The thickness of the surface protective coating layer 1 is more preferably 12 μm or more and 25 μm or less, and further preferably 15 μm or more and 20 μm or less.

[0048] (base film layer) The decorative sheet 10 of the present invention has a base film layer 2, which includes at least a decorative layer, a first olefin resin layer, and a primer layer. The base film layer 2 preferably contains a thermoplastic resin. The decorative sheet of the present invention having a base film layer containing a thermoplastic resin has excellent processability and is therefore highly suitable for roll forming and embossing. Examples of the thermoplastic resin include the resin components exemplified in each layer constituting the base film layer 2 described below. Examples of such a base film layer 2 include a decorative layer, a first olefin resin layer, a primer layer, a second olefin resin layer, a backer layer, and the like. FIG. 3 is a schematic cross-sectional view of a preferred example of a decorative material using the decorative sheet of the present invention. As shown in Figure 3, the decorative material 100 is formed by laminating a decorative sheet 10 having a surface protective coating layer 1 and a base film layer 2, and a substrate 20, and the base film layer 2 is a layer including a first olefin resin layer 3, a decorative layer 4, a second olefin resin layer 5, and a backer layer 6. The primer layer is preferably provided on one or both sides of the first olefin resin layer 3, for example. Each layer constituting the base film layer 2 will be described.

[0049] (First olefin resin layer) The first olefin resin layer 3 preferably has an indentation hardness of 100 MPa or more. When the indentation hardness of the first olefin resin layer 3 is 100 MPa or more, scratches on the decorative material can be more suitably prevented. The first olefin resin layer 3 more preferably has an indentation hardness of 115 MPa or more, and further preferably 130 MPa or more. Moreover, the first olefin resin layer 3 more preferably has an indentation hardness of 200 MPa or less, and further preferably 180 MPa or less. The indentation hardness of the first olefin resin layer 3 can be measured by the same method as described above.

[0050] The first olefin resin layer 3 is preferably a layer made of an olefin resin. Examples of the olefin resin include homopolymers of olefins such as ethylene, propylene, and butene; ethylene-propylene block copolymers and random copolymers; copolymers of at least one of ethylene and propylene with at least one other olefin such as butene, pentene, and hexene; and copolymers of at least one of ethylene and propylene with at least one other monomer such as vinyl acetate and vinyl alcohol. Among these, polyethylene and polypropylene are preferred, and polyethylene is more preferred, from the viewpoint of obtaining excellent scratch resistance and good bending processability.

[0051] The polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another comonomer copolymerizable with ethylene (for example, an α-olefin such as propylene, 1-butene, 1-hexene, or 1-octene, vinyl acetate, or vinyl alcohol). Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHMWPE), and cross-linked polyethylene (PEX). These polyethylenes may be used alone or in combination of two or more.

[0052] The polypropylene may be a homopolymer of propylene or a copolymer of propylene and another comonomer copolymerizable with propylene (for example, an α-olefin such as ethylene, 1-butene, 1-hexene, or 1-octene; vinyl acetate, vinyl alcohol, or the like). These polypropylenes may be used alone or in combination of two or more. In the present invention, a homopolymer of propylene (homopolypropylene) is particularly preferred from the viewpoint of excellent scratch resistance and bending processability.

[0053] The indentation hardness of the base film layer 2 can be appropriately set by making the first olefin resin layer 3 a microcrystalline olefin resin layer, for example.

[0054] The above-mentioned microcrystalline olefin resin layer can be obtained, for example, by adding a crystal nucleating agent to the olefin resin composition forming the first olefin resin layer 3, melting the composition, and then cooling the composition. In this case, the cooling method may be, for example, a chill roll method in which the material extruded from the die is brought into contact with a chill roll (chill roll) through which cooling water is passed during extrusion molding.

[0055] Examples of the crystal nucleating agent include metal salt-based crystal nucleating agents such as fatty acid metal salts, phosphonic acid metal salts, phosphate ester metal salts, benzoic acid metal salts, pimelic acid metal salts, and rosin metal salts; organic crystal nucleating agents such as fatty acid esters, aliphatic amides, benzylidene sorbitol, quinacridone, and cyanine blue; and inorganic crystal nucleating agents such as talc. The nucleating agent may be encapsulated in a nanoshell. By using a nucleating agent encapsulated in a nanoshell, the nucleating agent is more uniformly dispersed in the first olefin resin layer 3. This allows the indentation hardness to be easily and stably adjusted to a suitable value regardless of various conditions such as melting conditions and cooling conditions, and also provides excellent scratch resistance and good bending workability. As the nanoshell, those described in International Publication No. 2018 / 159660 and the like can be appropriately selected and used.

[0056] The content of the above-mentioned crystal nucleating agent in the first olefin resin layer 3 is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, even more preferably 0.03 to 1 part by mass, and particularly preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the resin component forming the first olefin resin layer 3. When the content of the nucleating agent is within the above range, it is easily dispersed uniformly in the resin forming the first olefin resin layer 3, the effect as a nucleating agent is easily obtained, the indentation hardness of the base film layer 2 can be suitably adjusted, and excellent scratch resistance and bending processability can be obtained.

[0057] From the viewpoint of obtaining excellent scratch resistance and bending workability, the thickness of the first olefin resin layer 3 is preferably 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, even more preferably 50 μm or more and 100 μm or less, and particularly preferably 55 μm or more and 85 μm or less. If the thickness of the first olefin resin layer 3 is less than 30 μm, the scratch resistance and impact resistance (especially dent resistance) may be poor, and the first olefin resin layer 3 may be stretched by the tension applied during printing or coating with a printing press. Furthermore, if the thickness of the first olefin resin layer 3 exceeds 120 μm, there is a risk that cracks or breakage may occur in the surface protective coating layer 1 during bending, and that impact resistance (particularly crack resistance) may be poor.

[0058] (Primer layer) The primer layer is provided mainly to improve the adhesion between the layers. In the decorative sheet 10 of the present invention, the primer layer can be provided, for example, on one or both sides of the first olefin resin layer 3, on one or both sides of the second olefin resin layer 5, or the like.

[0059] The primer layer can be formed, for example, from a resin composition in which a binder exemplified as a binder that can be used in the decorative layer is appropriately mixed with a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. Among these, it is preferable to use an olefin resin from the viewpoint of suitably improving adhesion.

[0060] From the viewpoint of improving adhesion, the thickness of the primer layer is preferably 0.2 μm or more and 20 μm or less, more preferably 0.5 μm or more and 15 μm or less, and even more preferably 1 μm or more and 12 μm or less.

[0061] (decorative layer) The decorative sheet 10 of the present invention can have a decorative layer 4 from the viewpoint of improving the design. The decorative layer 4 can be provided, for example, between the first olefin resin layer 3 and the second olefin resin layer 5, or between the first olefin resin layer 3 and the surface protective coating layer 1, or on the surface protective coating layer 1, or the like.

[0062] The decorative layer 4 may be, for example, a colored layer (a so-called solid layer) that covers the entire surface, or a patterned layer formed by printing various patterns using ink and a printing machine, or a combination of these. Furthermore, the decorative layer may be provided at multiple locations within the same layer, or may be provided in multiple layers rather than just one layer.

[0063] For example, when coloring and concealing the base color of the base material 20, a solid layer can be used to improve the design while concealing the color. From the viewpoint of further improving the design, a solid layer and a pattern layer may be combined, or, on the other hand, when making use of the base pattern of the decorative board base material, only a pattern layer may be provided without a solid layer.

[0064] The ink used for the decorative layer 4 is a mixture of a binder, a colorant such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc., as appropriate.

[0065] The binder is not particularly limited, and preferred examples thereof 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, cellulose acetate resin, etc. These binders can be used alone or in combination.

[0066] As the colorant, from the viewpoint of coloring and concealing the base color of the substrate 20 and improving the design, for example, inorganic pigments such as white pigment, 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, and phthalocyanine blue; metal pigments consisting of scaly foil flakes of aluminum, brass, etc.; and pearlescent pigments consisting of scaly foil flakes of titanium dioxide-coated mica, basic lead carbonate, etc. may be used.

[0067] When a pattern layer is provided as the decorative layer 4, the pattern may be a wood grain pattern, a stone pattern imitating the surface of rock such as a marble pattern (e.g., travertine marble pattern), a fabric pattern imitating a cloth or fabric-like pattern, a tiled pattern, a brickwork pattern, or a combination of these, such as marquetry or patchwork. These patterns can be formed by multicolor printing using the usual process colors of yellow, red, blue, and black, or by multicolor printing using spot colors, in which blocks of each color constituting the pattern are prepared.

[0068] The thickness of the decorative layer 4 may be selected appropriately depending on the desired pattern, but from the viewpoint of coloring and concealing the base color of the decorative board substrate and improving the design, it is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, and even more preferably 2 to 5 μm.

[0069] (Second olefin resin layer) The second olefin resin layer 5 is preferably a layer made of an olefin resin. Examples of the olefin resin that can form the second olefin resin layer 5 include the same olefin resins that can form the first olefin resin layer 3. Among these, polyethylene and polypropylene are preferred from the viewpoint of excellent scratch resistance and bending processability.

[0070] The second olefin resin layer 5 may be colored as needed. In this case, a colorant may be added to the olefin resin, and the pigments or dyes used in the decorative layer 4 may be used as the colorant.

[0071] From the viewpoint of excellent scratch resistance and bending processability, the thickness of the second olefin resin layer 5 is preferably 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, even more preferably 50 μm or more and 100 μm or less, and particularly preferably 55 μm or more and 95 μm or less.

[0072] (Backer layer) The decorative sheet 10 of the present invention may have a backer layer 6 on the bottom layer of the decorative sheet 10, that is, on the side of the decorative sheet 10 facing the second olefin resin layer 5. By providing the backer layer 6, it is possible to suitably prevent gouges, dents, and changes in gloss, and it is possible to suitably impart impact resistance.

[0073] Examples of the backer layer 6 include a synthetic resin backer layer and a foamed resin backer layer, and it is preferable that the backer layer 6 is provided as the bottom layer of the decorative sheet 10 (the side opposite to the side on which the surface protective coating layer 1 is laminated).

[0074] Examples of resins that can be used to form the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate (e.g., polyethylene terephthalate in which part of the ethylene glycol has been substituted with 1,4-cyclohexanedimethanol, diethylene glycol, or the like, known as PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, etc. These resins can be used alone or in combination of two or more.

[0075] The synthetic resin backer layer may contain hollow beads. The type, particle size, content, etc. of the hollow beads may be those described in JP 2014-188941 A.

[0076] Methods for forming the synthetic resin backing layer include calendar molding, extrusion molding of molten resin, etc. Among these, extrusion molding of molten resin is preferred, and for example, extrusion molding using a T-die is more preferred.

[0077] The foamed resin backing layer may be provided as a layer further below the synthetic resin backing layer (on the side opposite to the side having the uneven shape). The foamed resin backer layer may be that described in JP-A-2014-188941.

[0078] The backer layer preferably has a thickness of 100 μm or more. When the thickness of the backer layer is 100 μm or more, dents can be more effectively prevented and the film can have excellent impact resistance. The backer layer preferably has a thickness of 120 μm or more, and more preferably 200 μm or more. The upper limit of the thickness of the backer layer is preferably 1000 μm or less, more preferably 600 μm or less, and even more preferably 400 μm or less.

[0079] (others) In addition, in order to improve the adhesion between each layer, one or both surfaces of the first olefin resin layer 3 and the second olefin resin layer 5 may be subjected to a surface treatment such as a physical surface treatment by oxidation or roughening, or a chemical surface treatment.

[0080] (Decorative sheet manufacturing method) An example of a manufacturing method for the decorative sheet 10 of the present invention will be described using as an example a decorative sheet 10 having, in the thickness direction, a surface protective coating layer 1, a first olefin resin layer 3, a decorative layer 4, a second olefin resin layer 5, and a backer layer 6 in that order, which is one of the preferred embodiments of the decorative sheet 10 of the present invention.

[0081] First, a resin composition for forming the second olefin resin layer 5 is prepared, and the first olefin resin layer is formed by a method such as melt extrusion. Separately, a resin composition for forming the first olefin resin layer 3 is prepared, and the first olefin resin layer 3 is formed by a method such as melt extrusion. An uncured layer formed by applying a curable resin composition to the first olefin resin layer 3 is cured by heating or irradiating with ionizing radiation to form a surface protective coating layer 1.

[0082] Next, an adhesive is applied to at least one surface of the decorative layer 4 and the first olefin resin layer 3, and the decorative layer 4 and the first olefin resin layer 3 are attached so that they face each other, thereby producing a decorative sheet 10 having a surface protective coating layer 1, a first olefin resin layer 3, a decorative layer 4, and a second olefin resin layer 5 in that order. The backer layer 6 can be formed by a known method, for example, by laminating a backer layer 6 produced by a T-die extrusion method or the like and a second olefin resin layer 5 by thermal lamination or dry lamination via an adhesive.

[0083] In the above manufacturing method, after forming the decorative layer 4, the first olefin resin layer 3 is laminated by extrusion lamination, dry lamination, wet lamination, thermal lamination, etc. using a resin composition that forms the first olefin resin layer 3, and bonding and pressing the first olefin resin layer 3 together via an adhesive and / or a thermoplastic resin such as an acid-modified polyolefin resin.Next, an uncured layer formed on the first olefin resin layer 3 by applying a curable resin composition is cured by heating or irradiating with ionizing radiation to form the surface protective coating layer 1.This also allows the production of a decorative sheet having, in order, the second olefin resin layer 5, the decorative layer 4, the first olefin resin layer 3, and the surface protective coating layer 1.

[0084] The decorative layer 4 is formed by applying the ink used to form the decorative layer 4 onto the first olefin resin layer 3 or the second olefin resin layer 5 to provide a desired colored layer and / or patterned layer. The ink can be applied by a known method such as gravure printing, bar coating, roll coating, reverse roll coating or comma coating, preferably by gravure printing.

[0085] In forming the surface protective coating layer 1, the curable resin composition is applied preferably by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, or comma coating, more preferably by gravure coating, so that the thickness after curing is a predetermined thickness.

[0086] When an ionizing radiation resin composition is used to form the surface protective coating layer 1, the uncured resin layer formed by coating the resin composition is irradiated with ionizing radiation such as electron beams or ultraviolet rays to form a cured product, thereby forming the surface protective coating layer 1. When an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the resin used and the layer thickness, but it is usually preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. The irradiation dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected within the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used.

[0087] When ultraviolet light is used as the ionizing radiation, ultraviolet light having a wavelength of 190 to 380 nm is emitted. There are no particular limitations on the ultraviolet light source, and examples that can be used include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

[0088] When a thermosetting resin composition is used to form the surface protective coating layer 1, the resin composition may be cured by a heat treatment appropriate for the resin composition used to form the surface protective coating layer 1.

[0089] The primer layer can be formed by applying the resin composition that forms the primer layer using a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating.

[0090] Next, recesses having the above-described shape are formed in the surface protective coating layer 1. In consideration of ease of operation, it is preferable to form the recesses by embossing, which may be carried out by a conventional method using a known sheet-fed or rotary embossing machine.

[0091] The decorative sheet of the present invention having the above-described configuration has a predetermined recess on the surface of the surface protective coating layer opposite the base film layer side, which not only prevents gouges and dents but also prevents changes in gloss, and furthermore, makes it easy to wipe off dirt.

[0092] A decorative material in which the decorative sheet of the present invention is laminated on a substrate also constitutes one aspect of the present invention.

[0093] <Base material> Examples of the substrate 20 include at least one of wood substrates such as medium-density wood fiberboard, high-density wood fiberboard, particle board, softwood plywood, hardwood plywood, fast-growing wood plywood, cork sheet, and cork-containing composite substrates, and thermoplastic resin boards (resin boards whose main components are polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or foamed versions of these resins). The substrate 20 is preferably plywood. By using plywood as the base material 20, it is possible to suitably prevent gouges, dents, and changes in gloss.

[0094] Here, examples of coniferous trees include linden pine, larch, Hokkaido pine, cedar, cypress, pine, sequoia, spruce, etc. Examples of broad-leaved trees include lauan, china, birch, sen, beech, oak, meranti, etc. Furthermore, examples of fast-growing trees include poplar, falcata, acacia, camellia, eucalyptus, terminalia, etc.

[0095] When using wood plywood such as softwood plywood, hardwood plywood, or fast-growing wood plywood, the number of layers of wood veneers (number of plies) is not limited, but is usually preferably 3 to 7, and more preferably 5 to 7. In addition, there are no limitations on the adhesive used when producing the wood plywood, and a wide variety of known woodworking adhesives can be used.

[0096] Examples of the adhesive include adhesives containing as an active ingredient polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. Also included as thermosetting adhesives are melamine-based, phenol-based, urea-based (vinyl acetate-urea, etc.) adhesives, etc.

[0097] The thickness of the substrate 20 is not limited, but is preferably about 2 mm or more and 15 mm or less, and more preferably 2 mm or more and 12 mm or less.

[0098] The method for laminating the decorative sheet 10 of the present invention and the substrate 20 is not limited, and for example, a method of adhering them with an adhesive can be employed. The adhesive may be appropriately selected from known adhesives, such as polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, reactive hot melt adhesives such as urethane reactive hot melt (hereinafter referred to as "PUR adhesive"), butadiene-acrylonitrile rubber, neoprene rubber, and natural rubber. These adhesives may be used alone or in combination of two or more. [Example]

[0099] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0100] Example 1 A 60 μm thick colored polypropylene film was prepared as the second olefin resin layer, and a decorative layer (5 μm thick) was laminated on one surface of the film using a gravure printing machine. Next, a 48 μm thick, 50 MPa olefin-based film (random polypropylene, clear) was prepared as the first olefin resin layer, and a 12 μm thick primer layer (olefin resin layer) was formed on one side of the first olefin resin layer. An adhesive was applied to this primer layer, and the primer layer was then bonded to the decorative layer via the adhesive. A surface protective coating layer composition (urethane acrylate-based electron beam curable resin) was applied to the surface of the first olefin resin layer by gravure coating, and then cured by irradiating with ionizing radiation (electron beam) to form a surface protective coating layer 15 μm thick and with an indentation hardness of 150 MPa. Furthermore, the surface was embossed with heat and pressure from the side where the surface protective coating was formed to form a wood grain vessel pattern (groove-like) (depressions). The density of the depressions formed was 25%, the maximum depth was 50 μm, and the average width was 350 μm. Thereafter, a 120 μm thick olefin film (homopolypropylene) was attached to the back surface of the second olefin resin layer (the surface opposite to the side having the decorative layer) to form a backer layer, thereby producing a decorative sheet. The decorative material of Example 1 was produced by bonding the decorative sheet and the substrate together via an adhesive (so that the side of the decorative sheet opposite to the side having the surface protective coating layer was in contact with the substrate).

[0101] Example 2 A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 25%, a maximum depth of 50 μm and an average width of 200 μm.

[0102] Example 3 A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 47%, a maximum depth of 50 μm, and an average width of 350 μm.

[0103] Example 4 A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 25%, a maximum depth of 80 μm and an average width of 350 μm.

[0104] Example 5 A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 15%, a maximum depth of 40 μm and an average width of 350 μm.

[0105] (Comparative Example 1) A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 5%, a maximum depth of 40 μm and an average width of 250 μm.

[0106] (Comparative Example 2) A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 35%, a maximum depth of 100 μm and an average width of 350 μm.

[0107] (Comparative Example 3) A decorative material was produced in the same manner as in Example 1, except that groove-shaped recesses were formed on the surface of the surface protective coating layer so as to have a density of 30%, a maximum depth of 10 μm and an average width of 250 μm.

[0108] <Evaluation method> (indentation hardness) The indentation hardness of the surface protective coating layer and the first olefin resin layer was measured by the method described in the specification.

[0109] (1) Pencil hardness test The decorative materials prepared in the examples and comparative examples were tested using a pencil with a hardness of 2H in accordance with JIS K5600 and evaluated for the following items. The results are shown in Table 1. The overall evaluation shown in Table 1 was that all evaluations were "+ / -" or higher. (gloss change) +: Cannot be visually identified + / -: Slightly noticeable to the naked eye but not noticeable -:Easily distinguishable and noticeable (Gouge wound) +: Scratch length less than 2mm + / -: Scratch length is 2mm or more and less than 3mm -: Scratch length exceeds 3mm (Dent) +: No visible dents + / -: A slight dent is visible to the naked eye, but it is not noticeable. -: Dents are easily visible and noticeable

[0110] (2) Dirt-removal properties Red crayon was applied three times to an area of ​​1 cm x 7 cm on the surface of the decorative materials prepared in the Examples and Comparative Examples, and then left for 15 minutes. The material was then wiped off with a tissue soaked in ethanol, and the wiping ability was evaluated according to the following criteria. A score of 2 or higher was considered acceptable. 4: Can be wiped off in 20 round trips or less 3: Wipe without limit and no color remains 2: Wiped unlimited times, very slight color residue 1: Unlimited wiping and color remains

[0111] [Table 1]

[0112] The decorative materials produced in the examples were all rated "+ / -" or better in the evaluations of gloss change, gouges, and dents, and were therefore deemed to be acceptable overall. In particular, the decorative materials produced in Examples 1, 3 and 4, in which the indentation hardness of the surface protective coating layer was 250 MPa or more and the thickness of the surface protective coating layer was 15 to 30 μm, were excellent in all pencil hardness tests. On the other hand, the decorative material produced in Comparative Example 1, in which the density of recesses was 5%, was unable to prevent gloss changes, and the decorative material produced in Comparative Example 2, in which the maximum depth of recesses was 100 μm, was inferior in dirt wiping ability.Furthermore, the decorative material produced in Comparative Example 3, in which the maximum depth of recesses was 10 μm, was unable to prevent gloss changes. [Industrial Applicability]

[0113] According to the present invention, it is possible to obtain a decorative sheet and a decorative material that have extremely excellent scratch resistance that can prevent gloss changes and also have excellent stain wiping properties. [Explanation of symbols]

[0114] 1. Surface protection coating layer 2 Base film layer 3. First olefin resin layer 4. Cosmetic layer 5. Second olefin resin layer 6 Backer Tier 10 Decorative Sheet 20 Base material 30 Measurement samples 31 Berkovich indenter 32 Load direction 100 Cosmetic Materials

Claims

1. A decorative sheet comprising a surface protective coating layer and a base film layer, the surface protective coating layer has a recess on the surface opposite to the side on which the base film layer is formed, the base film layer includes at least a decorative layer, a first olefin resin layer, and a primer layer, The recesses have a density of 15% or more and 47% or less when viewed from the surface of the decorative sheet, an average width of 200 μm or more and 350 μm or less, and a maximum depth of 40 μm or more and 80 μm or less, The surface protective coating layer has an indentation hardness of 100 MPa or more and 300 MPa or less. A decorative sheet characterized by:

2. The decorative sheet according to claim 1 , wherein the base film layer contains a thermoplastic resin.

3. 3. The decorative sheet according to claim 1, wherein the total thickness of said decorative sheet is 200 μm or more.

4. 4. The decorative sheet according to claim 1, wherein the surface protective coating layer has a thickness of 10 μm or more.

5. A decorative material comprising the decorative sheet according to any one of claims 1 to 4 laminated on a substrate.

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