Cosmetic sheet and cosmetic material

Abstract

To provide a decorative sheet which has sufficient touch feeling, is excellent in scratch resistance, abrasion resistance and stain resistance, and prevents deterioration in productivity, and a decorative material using the decorative sheet.SOLUTION: A decorative sheet has at least a pattern layer, a transparent resin layer and a surface protective layer in this order on a base material sheet, in which the decorative sheet has a recess on a surface on a side having the surface protective layer, indentation hardness of the transparent resin layer is 40 MPa or more, indentation hardness of the surface protective layer is 100 MPa or more, and the recess satisfies following conditions (A) to (D). (A) Density of the recess when the decorative sheet is viewed in plane is 20% or more. (B) An average depth of the recess is 40 μm or more. (C) A ratio (average width / average depth) of an average width to an average depth of the recess is 5 or more. (D) The maximum depth of the recess is 80% or less to a total thickness of the decorative sheet.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] When it is desired to decorate the members used in building materials, furniture, household appliances, etc., decorative materials are generally used. Normally, in a decorative material, in a configuration where only a pattern layer is directly provided on a base material, surface performances such as scratch resistance, stain resistance, and weather resistance are insufficient. Therefore, a cosmetic sheet in which a transparent resin film is laminated on the pattern layer provided on the base material is laminated to impart surface performance.

[0003] In such a cosmetic sheet, a method of forming recesses on the surface of the cosmetic sheet may be used for the purpose of imparting a tactile sensation close to that of real wood grain or the like.

[0004] For example, in Patent Document 1, there is disclosed a cosmetic sheet having at least a transparent resin layer and a surface protective layer in this order on a base material sheet, (1) an uneven pattern is formed on the surface of the cosmetic sheet, (2) the ten-point average roughness Rz (JIS B 0601: 1982) of the uneven pattern is 40 μm or more, (3) the thickness of the transparent resin layer is 70 μm or more, and (4) the Martens hardness of the transparent resin layer is less than 30 N / mm 2 is disclosed, characterized in that it is a cosmetic sheet.

[0005] However, in the conventional cosmetic sheet, the following problems (1) to (4) caused by the recesses have not been sufficiently studied, and there is room for further improvement. (1) It is still not sufficient to satisfy the tactile sensation required by the current market. (2) The scratch resistance and abrasion resistance may be reduced due to the catching of the recesses. (3) It may be difficult to remove the dirt at the bottom of the recesses (reduction of stain resistance). (4) When forming the recesses, the cosmetic sheet may be greatly deformed, resulting in sheet breakage or the like and a decrease in productivity.

Prior Art Documents

Patent Document

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention solves the above-described problems, has a sufficient touch feeling, is excellent in scratch resistance, abrasion resistance, and stain resistance, and provides a decorative sheet whose productivity does not decrease, and a decorative material using the decorative sheet. The purpose is to do.

Means for Solving the Problems

[0008] The inventors of the present invention earnestly studied to solve the above-described problems, and appropriately imparted the indentation hardness of the transparent resin layer and the surface protective layer constituting the decorative sheet, and the density of the recesses formed on the surface of the decorative sheet, The shape of the recess (width in the frontage, average depth, and maximum depth) is set within an appropriate range, so that it has a touch feeling required by the current market, and also solves the above-described problems of scratch resistance, abrasion resistance, stain resistance, and productivity. As a result, the present invention has been completed.

[0009] That is, the present invention is a decorative sheet having at least a pattern layer, a transparent resin layer, and a surface protective layer in this order on a base material sheet, and the decorative sheet has recesses on the surface on the side having the surface protective layer, The indentation hardness of the transparent resin layer is 40 MPa or more, the indentation hardness of the surface protective layer is 100 MPa or more, and the recess satisfies the following conditions (A) to (D). It is a decorative sheet characterized by that. (A) The density of the recesses when the decorative sheet is viewed in plan is 20% or more. (B) The average depth of the recesses is 40 μm or more. (C) The ratio of the average width to the average depth of the recesses (average width / average depth) is 5 or more. (D) The maximum depth of the concave portion is 80% or less with respect to the total thickness of the decorative sheet.

[0010] In the decorative sheet of the present invention, it is preferable that the density of the concave portion is 35% or less. Further, it is preferable that the average depth of the concave portion is 60 μm or more. Further, it is preferable that the ratio of the average width to the average depth (average width / average depth) of the concave portion is 6 or more. Further, it is preferable that the surface protective layer contains an antiviral agent. Further, it is preferable that the maximum depth of the concave portion is 65% or less with respect to the total thickness of the decorative sheet. The present invention also provides a decorative material characterized in that the decorative sheet of the present invention and a base material are laminated.

Advantages of the Invention

[0011] The present invention can provide a decorative sheet having a sufficient touch feeling, excellent scratch resistance, abrasion resistance, and stain resistance, and not reducing productivity, and a decorative material using the decorative sheet.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the cosmetic sheet and the cosmetic material of the present invention will be described. In the following description, the lower and upper limits of the numerical range represented by "~" mean "above and below" (for example, if it is α~β, it means α or more and β or less).

[0014] <Cosmetic sheet> The cosmetic sheet of the present invention is a cosmetic sheet having a pattern layer, a transparent resin layer, and a surface protective layer in this order on a base sheet, and the cosmetic sheet has a concave portion on the surface on the side having the surface protective layer, the indentation hardness of the transparent resin layer is 40 MPa or more, the indentation hardness of the surface protective layer is 100 MPa or more, and the concave portion is characterized by satisfying the following conditions (A) to (D). (A) The density of the concave portions when the cosmetic sheet is viewed in plan is 20% or more. (B) The average depth of the concave portions is 40 μm or more. (C) The ratio of the average width to the average depth of the concave portions (average width / average depth) is 5 or more. (D) The maximum depth of the concave portions is 80% or less with respect to the total thickness of the cosmetic sheet.

[0015] Fig. 1(a) is a schematic cross-sectional view of the cosmetic sheet of the present invention, and Fig. 1(b) is a schematic plan view of the cosmetic sheet of the present invention. As shown in Fig. 1(a), the cosmetic sheet 10 of the present invention includes a surface protective layer 1, a transparent resin layer 2, a pattern layer 3, and a base sheet 4. As shown in Figs. 1(a) and (b), the cosmetic sheet 10 of the present invention includes a surface protective layer 1, a transparent resin layer 2, a pattern layer 3, and a base sheet 4, and the cosmetic sheet 10 has a groove-shaped concave portion a on the surface on the side having the surface protective layer.

[0016] (Concave portion) A groove-shaped recess a is formed on the surface of the cosmetic sheet 10 of the present invention. The recess a only needs to be present at least in the surface protective layer 1 of the cosmetic sheet 10. The depth of the recess a may remain within the surface protective layer 1, or may reach the base material sheet 4 described later, or there may be a case where it protrudes and appears on the underlying layer or the back surface. From the viewpoint of obtaining an excellent texture (tactile sensation), it is preferable that not only those remaining within the surface protective layer 1 but also those reaching the base material sheet 4 and those reaching the transparent resin layer 2 described later are combined.

[0017] Examples of the pattern of the recess a include a wood grain board conduit groove, a stone slab surface unevenness, a cloth surface texture, a satin finish, a grained surface, a hairline, a multi-line groove, etc. From the viewpoint of improving the design property, the pattern of the recess a is preferably a pattern synchronized with the pattern of the pattern layer 3 described later. For example, when the pattern layer 3 has a wood grain pattern, if a wood grain board conduit groove is selected as the pattern of the recess and the wood grain of the pattern layer 3 and the wood grain of the recess are synchronized, a more realistic, textured, and high-class cosmetic sheet can be obtained.

[0018] (Density of the recess) In the cosmetic sheet 10 of the present invention, the density of the recess a is 20% or more when the cosmetic sheet is viewed in a plan view. When the density is less than 20%, the tactile sensation of the cosmetic sheet 10 becomes insufficient. The density of the above-mentioned recess a is preferably 45% or less. If it exceeds 45%, the scratch resistance may decrease. The preferable lower limit of the density of the above-mentioned recess a is 25%, the more preferable upper limit is 40%, and the further preferable upper limit is 35%. In addition, in this specification, the "density of the recess" is measured by the following method.

[0019] (1) As shown in FIG. 4, the cosmetic sheet of the present invention is cut into 100 mm × 100 mm to prepare a sample 40, and 10 measurement regions 41 are arbitrarily selected on the surface of the sample 40. At this time, the measurement regions 41 are selected at equal intervals so as not to be biased in the sample 40. In the measurement of the density of the concave portions, the size of one measurement region 41 shall be 20 mm × 15 mm. (2) In each selected measurement region 41, measure the density of the concave portions by the following method. (2-1) Measurement environment Measuring device: Shape analysis laser microscope "VK-X1000" manufactured by KEYENCE Analysis software: Adobe Photoshop manufactured by Adobe (2-2) Measurement procedure (i) Place the sample 40 on the sample stage of the VK-X1000 and focus. (ii) Select one measurement region 41 and measure the surface shape. (iii) Remove the undulations from the measured surface shape. (iv) Change the height display of the measured data with the undulations removed to black and white. (v) Save the obtained image as a TIF image, import it into Adobe Photoshop, and then perform image trimming. The trimming is performed evenly around the original image so that the vertical and horizontal lengths are 90% of the image before processing. (vi) In the image after trimming, select the portion corresponding to the concave portions and measure the area (number of pixels) occupied by the concave portions in the image. Specifically, (a) Select the darkest cell (K value: 100%) on the image. (b) Perform the process of color gamut specification (select cells of a color close to the specified color). Adjust the allowable amount of color gamut specification (parameter for judging color difference) in order to specify only the concave portions. Make sure that most of the concave portions can be selected and almost no flat surfaces (non-concave portions) are selected. (c) Measure the number of pixels in the area specified in (b). (vii) Calculate the density (%) of the concave portions in one measurement region 41 by the following formula.

Equation

[0020] (Shape of the concave portion) In the cosmetic sheet 10 of the present invention, the average depth of the concave portion a is 40 μm or more. If the average depth of the concave portion a is less than 40 μm, the touch feeling of the cosmetic sheet 10 becomes insufficient. The average depth of the concave portion a is preferably 60 μm or more, more preferably 70 μm or more, and still more preferably 80 μm or more.

[0021] In the cosmetic sheet 10 of the present invention, the ratio of the average width to the average depth of the concave portion a (average width / average depth) is 5 or more. If the above ratio (average width / average depth) is 5 or less, the scratch resistance and stain resistance decrease. The above ratio (average width / average depth) is preferably 5.5 or more, more preferably 6 or more, still more preferably 6.5 or more, and particularly preferably 7 or more. Also, from the viewpoint of suitably imparting the touch feeling of the surface of the cosmetic sheet 10, the above ratio (average width / average depth) is preferably less than 30.

[0022] In the cosmetic sheet 10 of the present invention, the average width of the concave portion a is not particularly limited as long as it satisfies the above ratio (average width / average depth). For example, it is preferably 300 μm or more, more preferably 400 μm or more, and still more preferably 500 μm or more. Also, the preferable upper limit is 1000 μm.

[0023] In the cosmetic sheet 10 of the present invention, the maximum depth of the concave portion a is 80% or less with respect to the total thickness of the cosmetic sheet 10. If the maximum depth of the concave portion a exceeds 80% with respect to the total thickness of the cosmetic sheet 10, sheet breakage is likely to occur and productivity decreases. In the cosmetic sheet 10 of the present invention, the maximum depth of the concave portion a is preferably 75% or less, more preferably 70% or less, and still more preferably 65% or less with respect to the total thickness of the cosmetic sheet 10.

[0024] In the cosmetic sheet 10 of the present invention, the maximum depth of the concave portion a is preferably 60 μm or more. When the maximum depth of the concave portion a is 60 μm or more, the touch feeling of the cosmetic sheet 10 can be suitably imparted. The maximum depth of the concave portion a is more preferably 70 μm or more, and still more preferably 80 μm or more. From the viewpoint of suitably imparting stain resistance, the upper limit of the maximum depth of the concave portion a is preferably 130 μm or less, and more preferably 120 μm or less.

[0025] In this specification, the "average width of the concave portion" is measured by the following method. (1) As shown in FIG. 4, the cosmetic sheet of the present invention is cut into 100 mm × 100 mm to produce a sample 40, and ten measurement regions 41 are arbitrarily selected on the surface of the sample 40. At this time, the measurement regions 41 are selected at equal intervals so as not to be biased in the sample 40. In the measurement of the average width of the concave portion, the size of one measurement region 41 is 4 mm × 4 mm. (2) In each of the selected measurement regions 41, the average width of the concave portion is measured by the following method. (2-1) Measurement environment Measuring device: Shape analysis laser microscope "VK-X1000" manufactured by KEYENCE Corporation (2-2) Measurement procedure (i) Place the sample 40 on the sample stage of the VK-X1000 and focus. (ii) Select one measurement region 41 and measure the surface shape. (iii) Remove the undulations from the measured surface shape. (iv) Measure the width of the concave portion in one measurement region from the image after removing the undulations. First, select three points for the recesses to be measured according to the following criteria. (A) It is a recess. (B) Two or more recesses do not overlap each other. (C) The aspect ratio (length of the major axis / length of the minor axis) of the recess is 10 or more. The "length of the major axis" is the length between the two maximum points on the contour drawn by the recess. The "length of the minor axis" is the length between the two maximum points in the direction perpendicular to the major axis on the contour drawn by the recess. In the groove-shaped recess shown in FIG. 5, the length of the broken line is the "length of the major axis", and the length of the thin line is the "length of the minor axis". Based on the above criteria, in the recesses shown in FIG. 5, A-1, B-1, C-1, C-2, and D can be selected because they all satisfy the above criteria (A) to (C). Although the whole of 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. The recess B-2 has an aspect ratio of 10 or more, but since its whole is not included in the measurement area and its maximum width is near the edge of the measurement area, it can be selected only when there are no other selectable recesses. On the other hand, the recesses B-3, E-1, and E-2 cannot be selected because their aspect ratios are less than 10, and the recess F cannot be selected because two recesses overlap. In the recesses selected above, select the place where the width is maximum and measure its length. At this time, the direction of the length of the width to be measured is parallel to the minor axis of the groove-shaped recess. After measuring the lengths of the widths of the groove-shaped recesses at the three selected points, the numerical value obtained by averaging them is defined as the width of the recess in one measurement area. (v) Calculate the "average width of the recesses" in the cosmetic sheet of the present invention by averaging the numerical values obtained by performing the procedures of (i) to (iv) for all the measurement areas 41 (a total of 10 points) where the procedures are selected.

[0026] In this specification, the "average depth of the recesses" and the "maximum depth of the recesses" are measured by the following method. Perform the procedures of (i) to (iii) similar to the above "average width of the recesses". (vi) Select three groove-shaped recesses whose depths are measured according to the same criteria as the "average width of the recesses". (vii) Perform smoothing (condition: ±8) on the image data obtained in (iii). (viii) Measure the maximum depth of the selected recess. Here, the "maximum depth" refers to the maximum value of the distance parallel to the thickness direction from the bottom of the recess to the flat surface of the surface. After measuring the maximum depth of the three selected groove-shaped recesses, the largest among the three points is taken as the maximum depth of the groove-shaped recess in the measurement area 1. (ix) The average depth can be calculated from the average value of the depths of the recesses obtained by performing the procedures of (i) to (viii) in all the selected measurement areas 41 (a total of 10 points). Also, the largest of the recesses obtained in the above measurement areas 41 (a total of 10 points) is taken as the "maximum depth of the recess" in the cosmetic sheet of the present invention.

[0027] (Total thickness) The cosmetic sheet 10 of the present invention preferably has a total thickness of 130 μm or more. If the total thickness of the cosmetic sheet 10 is less than 130 μm, the productivity of the sheet may decrease. The cosmetic sheet 10 more preferably has a total thickness of 150 μm or more, and even more preferably 160 μm or more. The upper limit of the total thickness of the cosmetic sheet 10 is not particularly limited, but is preferably 500 μm or less, and more preferably 400 μm or less.

[0028] Here, the total thickness of the cosmetic sheet 10 will be described. FIG. 2(a) is a schematic cross-sectional view of the cosmetic sheet of the present invention, and FIG. 2(b) is a schematic cross-sectional view of the cosmetic sheet of the present invention according to another form. When the cosmetic sheet 10 of the present invention has recesses only on one surface, as shown in FIG. 2(a), the length in the thickness direction from the surface A to the surface B is the "total thickness" of the cosmetic sheet 10. On the other hand, even when the cosmetic sheet 10 of the present invention has recesses on one surface and protrusions B' on the other surface, as shown in FIG. 2(b), the length in the thickness direction from the surface A to the surface B, which is a smooth surface, is the "total thickness" of the cosmetic sheet 10. Next, each layer constituting the cosmetic sheet 10 will be described.

[0029] (Surface protective layer) The cosmetic sheet 10 of the present invention has a surface protective layer 1. The surface protective layer 1 preferably has an indentation hardness of 100 MPa or more. When the indentation hardness of the surface protective layer 1 is less than 100 MPa, sufficient scratch resistance may not be imparted. The surface protective 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 layer 1 preferably has an indentation hardness of 300 MPa or less, and more preferably 290 MPa or less. When the indentation hardness of the surface protective layer 1 exceeds 300 MPa, it becomes brittle, and cracks may easily occur during handling of the cosmetic sheet 10 or during embossing for imparting design properties.

[0030] In this specification, the "indentation hardness" of each layer is indicated by the nano-indentation hardness measured using a surface film physical property tester Tribo Indenter (registered trademark) "TI-950" (manufactured by HYSITRON). The method for measuring the indentation hardness (HIT) of each layer using the Tribo Indenter (registered trademark) "TI-950" is as follows.

[0031] (1) Using the Berkovich indenter 31 shown in Fig. 6(a), as shown in Fig. 6(b), the Berkovich indenter 31 is pushed into the measurement sample 30 under the following pressing conditions in the arrow direction of the load application direction 32. From the triangular pyramid-shaped geometric shape formed on the surface, the "contact projected area (Ap) (mm 2 )" corrected by the method standard of the apparatus is calculated, and the hardness is obtained by dividing the maximum test load (Fmax) by the Ap. That is, HIT = Fmax / Ap. (2) Here, the indentation conditions are as follows at room temperature (laboratory environmental temperature). As shown in Fig. 6(c), for the surface protective layer 1, first, a load from 0 to 100 μN is applied in 10 seconds (i.e., 10 μN / s), then a load of 100 μN (Fmax) is maintained for 5 seconds, and finally, the unloading from 100 to 0 μN is performed in 10 seconds. For the transparent resin layer 2 described later, first, a load from 0 to 50 μN is applied in 5 seconds (i.e., 10 μN / s), then a load of 50 μN (Fmax) is maintained for 5 seconds, and finally, the unloading from 50 to 0 μN is performed in 10 seconds. Normally, since the indentation depth (h) is about 100 to 150 nm, the thickness of the layer serving as the measurement sample in the indentation direction may be 1.0 μm or more (preferably 1.5 μm or more). Ap is calculated by 24.50〔hmax - ε(hmax - hr)〕 2 (where ε is a correction coefficient depending on the geometric shape of the indenter, and hr is the depth of the geometric shape of the triangular pyramid remaining on the surface after unloading). (3) When measuring the hardness, in order to avoid the influence of the hardness of the layers other than the layer serving as the measurement sample 30, the hardness of the cross-section of the layer to be measured is measured. That is, the decorative sheet is embedded with a resin (a cold-curing type two-component epoxy resin), left to cure at room temperature for 24 hours or more, and after curing, the cured embedded sample is mechanically polished to expose the cross-section of the layer to be measured. 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 (at a position avoiding the fine particles such as fillers if the fine particles are contained in the layer). (4) For each layer, 10 indentation hardness values are measured so that no bias occurs, and the average value of the 10 points is defined as the "indentation hardness of the surface protective layer 1" and the "indentation hardness of the transparent resin layer 2", respectively.

[0032] From the viewpoint of improving the surface properties such as stain resistance, scratch resistance, and chemical resistance of the decorative sheet 10 of the present invention and further satisfying the above-described indentation hardness, the surface protective layer 1 is preferably made of a cured product of a curable resin composition. Examples of the above-mentioned curable resin composition include resin compositions containing curable resins such as thermosetting resins, two-component curable resins, and radiation curable resins. From the viewpoint of obtaining more excellent surface properties, resin compositions containing two-component curable resins and radiation curable resins are preferred as the curable resin.

[0033] Examples of the above-mentioned thermosetting resin include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, amino alkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins, silicone resins, polysiloxane resins, and the like.

[0034] To the above-mentioned thermosetting resin, curing agents such as crosslinking agents and polymerization initiators, and polymerization accelerators can be added. For example, as the curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resins and polyurethane resins, etc., organic amines can be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide, radical initiators such as azoisobutyronitrile can be added to unsaturated polyester resins.

[0035] Examples of the method for forming the surface protection layer 1 with the above-mentioned thermosetting resin include a method of applying a solution of the thermosetting resin by a coating method such as a roll coating method or a gravure coating method, and then drying and curing it.

[0036] The above-mentioned two-component curable resin is not particularly limited as long as it is a resin cured by a main agent and a curing agent. Preferably, a two-component curable urethane resin having a polyol (polyhydric alcohol) as the main agent and an isocyanate curing agent as the curing agent can be mentioned.

[0037] Examples of the above-mentioned main agent preferably include polyols such as polyethylene glycol, polypropylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol; polyols having a hydroxyl group as a functional group such as acrylic polyol, polyester polyol, polyether polyol; and the like. These can be used alone or in combination of two or more.

[0038] As the above-mentioned isocyanate curing agent, conventionally known compounds may be appropriately used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate; aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate; and the like polyisocyanates are used. In addition, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimer, etc. are also used.

[0039] The above-mentioned radiation-curable resin is a resin that cures by irradiating ionizing radiation, that is, electromagnetic waves or charged particle beams having energy quanta capable of polymerizing or crosslinking molecules, for example, ultraviolet rays (UV) or electron beams (EB), and in addition, electromagnetic waves such as X-rays and γ-rays, charged particle beams such as α-rays and ion beams. Specifically, as the radiation-curable resin, it can be appropriately selected and used from commonly used polymerizable monomers, polymerizable oligomers, and prepolymers.

[0040] As the above-mentioned polymerizable monomer, for example, (meth)acrylate-based monomers having a radically polymerizable unsaturated group in the molecule are preferable, and among them, polyfunctional (meth)acrylate monomers are preferred. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. For example, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferably mentioned. These (meth)acrylate monomers can be used alone or in combination of two or more.

[0041] Examples of the above-mentioned polymerizable oligomers include oligomers having a radically polymerizable unsaturated group in the molecule, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and (meth)acrylate oligomers such as acrylic (meth)acrylate oligomers. These polymerizable oligomers can be used alone or in combination of two or more.

[0042] In addition to the above-mentioned curable resin, the above-mentioned curable resin composition may contain a dispersant or the like described later.

[0043] As additives, the above-mentioned curable resin composition can be added with an ultraviolet absorber, an ultraviolet shielding agent, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, a defoaming agent, a filler, a blocking preventive agent, a dispersant, a solvent, a deodorant, an antibacterial agent, an antiallergic agent, a fungicide, etc. within a range not impairing the object of the present invention. Among them, in order to improve weather resistance, it is preferable to contain weathering agents such as ultraviolet absorbers and light stabilizers. Also, in order to impart antiviral properties, it is preferable to contain an antiviral agent.

[0044] Examples of the above-mentioned ultraviolet absorber include benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, acrylonitrile-based, etc., and examples of the light stabilizer include hindered amine-based, acrylate-based, oxamide-based, cyanoacrylate-based, etc.

[0045] The above-mentioned surface protection layer 1 can contain a dispersant. Examples of the above-mentioned dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicone oils, waxes, modified resins, etc. Further, the nanoshells described in International Publication No. 2018 / 159660 etc. can also be preferably used. These dispersants can be used alone or in combination of two or more.

[0046] The content of the above dispersant is preferably 0.01 part by mass or more and 30 parts by mass or less, more preferably 0.05 part by mass or more and 15 parts by mass or less, still more preferably 0.1 part by mass or more and 10 parts by mass or less, and particularly preferably 0.3 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin component forming the surface protection layer 1.

[0047] From the viewpoint of improving scratch resistance, the surface protection layer 1 preferably contains inorganic fine particles. Examples of the inorganic fine particles include silica, alumina, aluminosilicate, kaolinite, calcium carbonate, barium sulfate, and glass. Also, by controlling the type and content of the inorganic fine particles, the indentation hardness of the surface protection layer 1 can be adjusted.

[0048] The average particle diameter 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 still more preferably 2 μm or more and 15 μm or less. The average particle diameter of the inorganic fine particles is the 50% particle diameter (d50: median diameter) when the particles in the solution are measured by the dynamic light scattering method and the particle size distribution is represented by the volume cumulative distribution. The 50% particle diameter can be measured, for example, using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.).

[0049] 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 still more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component forming the surface protection layer 1.

[0050] The surface protection layer 1 preferably contains an antiviral agent. Here, the term "antiviral" means not only decomposing the virus but also suppressing its growth or generation. In addition, the antiviral agent may act not only on viruses but also on bacteria, molds, etc., and not only sterilize, disinfect, bacteriostatize or sterilize them, but also suppress their growth or generation (for molds, mildew removal, mildew prevention, etc.). By containing the above antiviral agent in the surface protective layer 1, the antiviral property can be imparted to the cosmetic sheet. The method of incorporating the antiviral agent into the surface protective layer 1 is not particularly limited. For example, the antiviral agent may be incorporated into the above curable resin composition.

[0051] Generally, the above antiviral agents can be roughly classified into organic and inorganic types. Examples of organic antiviral agents include quaternary ammonium salt-based, quaternary phosphonium salt-based, pyridine-based, pyrithione-based, benzimidazole-based, organic iodine-based, isothiazoline-based, anionic-based, ether-based, etc. Examples of inorganic antiviral agents include those in which metal ions such as silver, copper, and zinc are supported on zeolite, apatite, zirconia, glass, molybdenum oxide, etc.

[0052] Among the above organic antiviral agents, benzimidazole-based antiviral agents or anionic-based antiviral agents that maintain a particulate shape are preferably used. Maintaining a particulate shape means existing in the form of particles without dissolving in the curable resin composition (ink before curing) of the surface protective layer 1. Therefore, in the process of forming the surface protective layer 1, it is possible to easily unevenly distribute the particles of the imidazole-based compound, the particles of the compound, or the particles of the anionic compound. By unevenly distributing the particles of the imidazole-based compound or the anionic compound on the outermost surface side of the surface protective layer 1, the addition amount of the antiviral agent required to obtain a predetermined antiviral property can be suppressed, so that it is easy to suppress the decrease in the scratch resistance of the surface protective layer 1.

[0053] As the above-mentioned anionic antiviral agent, those containing, for example, a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound are preferred. In addition, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one structure among the structures of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all the structures. This is because there are two types of viruses, with or without an envelope, and it is considered that the structures of antiviral agents that can effectively inhibit the activity of each are different. For example, if only the effect on influenza virus, which is a non-enveloped virus, is expected, it may only contain a styrene polymer derivative compound, and among them, if only a styrene resin alone is contained, sufficient effects can be obtained.

[0054] As the above-mentioned inorganic antiviral agent, from the viewpoint of having no biological toxicity and excellent safety, a silver-based antiviral agent is preferred. Among them, a phosphate-based glass silver-supported compound or a silver zeolite compound, and a molybdenum oxide silver double salt compound are more preferred because they can exhibit antiviral performance even in a small amount, so the addition amount can be suppressed.

[0055] The average particle diameter of the above-mentioned inorganic antibacterial agent and antiviral agent is preferably, for example, 0.1 to 10 μm. With the above average particle diameter, the above antibacterial agent and antiviral agent can be preferably dispersed, and antibacterial and antiviral properties can be preferably imparted without unevenness.

[0056] When adding the above silver-based antibacterial agent and antiviral agent to the above surface protective layer, discoloration may occur depending on the surface protective layer 1 (it may discolor due to heat or light in the state of the added paint, or may discolor due to heat or light after the formation of the above surface protective layer). In this case, it is possible to improve by adding an ultraviolet absorber, a light stabilizer, etc. in a timely manner. For example, for the above molybdenum oxide silver double salt compound, the use of a benzotriazole compound can be expected to have an effect of improving discoloration.

[0057] The content of the antiviral agent is preferably 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.05 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the resin component forming the surface protective layer 1.

[0058] The thickness of the surface protective layer 1 is preferably 10 μm or more and 30 μm or less. When the thickness of the surface protective layer 1 is 10 μm or more and 30 μm or less, scratch resistance and abrasion resistance can be preferably imparted, and furthermore, cracking of the cosmetic sheet 10 of the present invention can be preferably prevented, and productivity can also be improved. The thickness of the surface protective layer 1 is more preferably 12 μm or more and 25 μm or less, and even more preferably 15 μm or more and 20 μm or less.

[0059] (Transparent resin layer) The transparent resin layer 2 has an indentation hardness of 40 MPa or more. When the indentation hardness of the transparent resin layer 2 is less than 40 MPa, the scratch resistance of the cosmetic sheet 10 becomes insufficient. The transparent resin layer 2 more preferably has an indentation hardness of 45 MPa or more, and even more preferably 50 MPa or more. Also, the transparent resin layer 2 more preferably has an indentation hardness of 200 MPa or less, and even more preferably 180 MPa or less. The method for measuring the indentation hardness of the transparent resin layer 2 is the same as the method described above.

[0060] The transparent resin layer 2 is preferably a layer made of an olefin resin. Examples of the olefin resin include homopolymers of olefins such as ethylene, propylene, and butene; block copolymers and random copolymers of ethylene and propylene; copolymers of at least one of ethylene and propylene and at least one other olefin such as butene, pentene, and hexene; copolymers of at least one of ethylene and propylene and at least one other monomer such as vinyl acetate and vinyl alcohol; and the like. Among them, polyethylene and polypropylene are preferable, and polyethylene is more preferable, from the viewpoints of obtaining excellent scratch resistance and good bend processability.

[0061] The polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another comonomer copolymerizable with ethylene (for example, α-olefins such as propylene, 1-butene, 1-hexene, and 1-octene, vinyl acetate, vinyl alcohol, etc.). 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), crosslinked polyethylene (PEX), and the like. These polyethylenes may be used alone or in combination of two or more.

[0062] The polypropylene may be a homopolymer of propylene or a copolymer of propylene and another comonomer copolymerizable with propylene (for example, α-olefins such as ethylene, 1-butene, 1-hexene, and 1-octene; vinyl acetate, vinyl alcohol, etc.). These polypropylenes may be used alone or in combination of two or more. In the present invention, a homopolymer of propylene (homopolypropylene) is particularly preferable from the viewpoints of excellent scratch resistance and bend processability.

[0063] The transparent resin layer 2 can also be a microcrystalline olefin resin layer.

[0064] In order to obtain the above microcrystalline olefin resin layer, for example, it can be carried out by adding a crystal nucleating agent to the olefin resin composition for forming the transparent resin layer 2, melting it, and then cooling it. In this case, as the cooling method, for example, cooling by a chill roll method in which the material extruded from the die is brought into contact with a cooling roll (chill roll) through which cooling water passes during extrusion molding can be mentioned.

[0065] Examples of the above crystal nucleating agent include metal salt-based crystal nucleating agents such as fatty acid metal salts, metal salts of phosphonic acids, metal salts of phosphate esters, metal salts of benzoic acids, metal salts of pimelic acids, and metal salts of rosins; organic crystal nucleating agents such as fatty acid esters, aliphatic amides, benzylidene sorbitol, quinacridone, and cyanine blue; inorganic crystal nucleating agents such as talc; and the like. In addition, as the above crystal nucleating agent, those in which the above crystal nucleating agent is encapsulated in a nanoshell can also be used. By using a crystal nucleating agent encapsulated in a nanoshell, the crystal nucleating agent is more uniformly dispersed in the transparent resin layer 2, so that the indentation hardness can be easily and stably adjusted suitably regardless of various conditions such as melting conditions and cooling conditions, and excellent scratch resistance and good bend processability can be obtained. Note that as the above nanoshell, those described in International Publication No. 2018 / 159660 etc. can be appropriately selected and used.

[0066] The content of the above crystal nucleating agent in the transparent resin layer 2 is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, still more preferably 0.03 to 1 part by mass, and particularly preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass of the resin component forming the transparent resin layer 2. When the content of the above crystal nucleating agent is within the above range, it is likely to be uniformly dispersed in the resin forming the transparent resin layer 2, the effect as a crystal nucleating agent is easily obtained, the indentation hardness of the transparent resin layer 2 can be suitably adjusted, and excellent scratch resistance and bend processability can be obtained.

[0067] From the viewpoint of obtaining excellent scratch resistance and bendability, the thickness of the transparent resin layer 2 is preferably 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, still 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 transparent resin layer 2 is less than 30 μm, the scratch resistance and impact resistance (particularly dent resistance) may be inferior, and when printing or coating is performed with a printing machine, the transparent resin layer 2 may be stretched by the tension applied during printing. On the other hand, if the thickness of the transparent resin layer 2 exceeds 120 μm, there is a risk that cracks or breaks may occur in the surface protective layer 1 during bending, and the impact resistance (particularly crack resistance) may be inferior.

[0068] (Pattern layer) From the viewpoint of improving the design property, the decorative sheet 10 of the present invention can have a pattern layer 3. The pattern layer 3 can be provided, for example, between the transparent resin layer 2 and the base sheet 4, between the transparent resin layer 2 and the surface protective layer 1, or on the surface protective layer 1.

[0069] The pattern layer 3 may be, for example, a colored layer (so-called solid layer) covering the entire surface, a pattern layer formed by printing various patterns using ink and a printing machine, or a combination thereof. Furthermore, the pattern layer may be provided at a plurality of locations within the same layer, or may be provided not only in one layer but also in a plurality of layers.

[0070] For example, when concealing the base color of the base material described later, by using a solid layer, it is possible to conceal the coloring while improving the design property. From the viewpoint of further improving the design property, a solid layer and a pattern layer may be combined. On the other hand, when making use of the base pattern of the decorative board base material, only the pattern layer may be provided without using a solid layer.

[0071] As the ink used for the pattern layer 3, a mixture in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. are appropriately mixed in a binder is used.

[0072] There is no particular limitation on the above binder. For example, resins such as urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (a urethane-acrylic copolymer derived from a polymer having a carbonate bond in the polymer main chain and having two or more hydroxyl groups at the terminals and side chains (polycarbonate polyol)), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. are preferably used. These binders can be used alone or in combination of two or more.

[0073] As the above colorant, from the viewpoint of coloring and concealing the background color of the base material described later and improving the design property, for example, inorganic pigments such as white pigment, iron black, lead yellow, titanium yellow, valance, cadmium red, ultramarine blue, cobalt blue, etc.; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, etc.; metal pigments composed of flaky foil pieces such as aluminum and brass; pearlescent (pearl) pigments composed of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate can also be used as the colorant.

[0074] When having a pattern layer as the pattern layer 3, examples of the pattern include a wood grain pattern, a stone grain pattern imitating the surface of a rock such as a marble pattern (e.g., travertine marble pattern), a fabric pattern imitating a cloth pattern or a cloth-like pattern, a tile sticker pattern, a brick stack pattern, etc. There are also patterns such as marquetry and patchwork obtained by combining these. These patterns are formed by multicolor printing using ordinary process colors of yellow, red, blue, and black, and can also be formed by multicolor printing with special features such as preparing plates for individual colors constituting the pattern.

[0075] The thickness of the pattern layer 3 may be appropriately selected according to the desired pattern. From the viewpoint of coloring and concealing the background color of the decorative board base material and improving the design property, 0.5 to 20 μm is preferable, 1 to 10 μm is more preferable, and 2 to 5 μm is still more preferable.

[0076] (Base sheet) The base sheet 4 is preferably a layer made of an olefin resin. Examples of the olefin resin forming the base sheet 4 include the same olefin resins that can form the transparent resin layer 2. Among them, polyethylene and polypropylene are preferable from the viewpoints of excellent scratch resistance and bend processability.

[0077] The base sheet 4 may be colored as necessary. In this case, a colorant may be added to the above olefin resin. As the above colorant, the pigments or dyes used in the pattern layer 3 described above can be used.

[0078] From the viewpoints of excellent scratch resistance and bend processability, the base sheet 4 preferably has a thickness of 30 μm or more and 120 μm or less, more preferably 40 μm or more and 110 μm or less, still more preferably 50 μm or more and 100 μm or less, and particularly preferably 55 μm or more and 95 μm or less.

[0079] (Backer layer) The decorative sheet 10 of the present invention may include a backer layer on the lowermost layer of the decorative sheet 10, that is, on the side of the base sheet 4 of the decorative sheet 10. By providing the backer layer, damage resistance and abrasion resistance can be suitably prevented, and impact resistance can be suitably imparted.

[0080] Examples of the backer layer include a synthetic resin backer layer and a foamed resin backer layer, and it is preferably provided on the lowermost layer of the decorative sheet 10 (the side opposite to the side where the surface protection layer 1 is laminated).

[0081] Examples of the resin constituting the synthetic resin backing layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate [for example, polyethylene terephthalate in which a part of ethylene glycol is replaced with 1,4-cyclohexanedimethanol or diethylene glycol, etc., so-called trade name 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.

[0082] The synthetic resin backing layer may contain hollow beads. For the type, particle diameter, content, etc. of the above hollow beads, those described in JP-A-2014-188941 can be applied.

[0083] Examples of the method for forming the synthetic resin backing layer include calendar molding, extrusion molding of molten resin, etc. Among them, extrusion molding of molten resin is preferable, and for example, extrusion molding using a T-die is more preferable.

[0084] The foamed resin backing layer may be provided in a lower layer (opposite side to the side having the uneven shape) than the synthetic resin backing layer. For the foamed resin backing layer, those described in JP-A-2014-188941 can be applied.

[0085] The backing layer preferably has a thickness of 100 μm or more. When the thickness of the backing layer is 100 μm or more, dent scratches can be more preferably prevented, and the impact resistance can also be excellent. The backing layer more preferably has a thickness of 120 μm or more, and even more preferably 200 μm or more. As the upper limit of the thickness of the backing layer, 1000 μm or less is preferable, 600 μm or less is more preferable, and 400 μm or less is even more preferable.

[0086] (Others) The cosmetic sheet 10 of the present invention may have a primer layer. The primer layer is a layer provided mainly for improving the adhesion of each layer.

[0087] In the cosmetic sheet 10 of the present invention, the primer layer can be provided, for example, on one or both sides of the transparent resin layer 2, on one or both sides of the base sheet 4, or the like. Also, similar to the primer layer, in order to improve the adhesion of each layer, physical surface treatments such as an oxidation method and a roughening method, or surface treatments such as chemical surface treatments may be performed on one or both sides of the transparent resin layer 2 and the base sheet 4.

[0088] The primer layer can be formed, for example, of a resin composition in which a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. are appropriately mixed with the binders exemplified as the binders that can be used for the above-described decorative layer.

[0089] From the viewpoint of improving the adhesion, the thickness of the primer layer is preferably 0.2 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and even more preferably 1 μm or more and 5 μm or less.

[0090] (Method for manufacturing a cosmetic sheet) Regarding the method for manufacturing the cosmetic sheet 10 of the present invention, taking as an example the cosmetic sheet 10 having, in the thickness direction, a surface protective layer 1, a transparent resin layer 2, a pattern layer 3, and a base sheet 4, which is one of the preferred embodiments of the cosmetic sheet 10 of the present invention, an example of the manufacturing method will be described.

[0091] First, a resin composition for forming the base sheet 4 is prepared, and the transparent resin layer 2 is formed into a film by a method such as a melt extrusion method, and the pattern layer 3 is formed on the base sheet 4. Separately from this, a resin composition for forming the transparent resin layer 2 is prepared, and the transparent resin layer 2 is formed into a film by a method such as a melt extrusion method. On the transparent resin layer 2, a curable resin composition is applied to an uncured layer, and the uncured layer is cured by heating or irradiation with ionizing radiation to form the surface protective layer 1.

[0092] Next, an adhesive is applied to at least one surface of the pattern layer 3 and the transparent resin layer 2, and the pattern layer 3 and the transparent resin layer 2 are adhered so as to face each other, whereby the decorative sheet 10 having the surface protective layer 1, the transparent resin layer 2, the pattern layer 3, and the base material sheet 4 in this order can be manufactured. When forming the backing layer, for example, the backing layer produced by a method such as the T-die extrusion method and the base material sheet 4 can be laminated by a known method such as thermal lamination or dry lamination via an adhesive.

[0093] In the above manufacturing method, after forming the pattern layer 3, using the resin composition for forming the transparent resin layer 2, the transparent resin layer 2 is adhered and pressure-bonded and laminated by a method such as extrusion lamination, dry lamination, wet lamination, or thermal lamination through an adhesive and / or a thermoplastic resin such as an acid-modified polyolefin resin. Then, on the transparent resin layer 2, a curable resin composition is applied to an uncured layer, and the uncured layer is cured by heating or irradiation with ionizing radiation to form the surface protective layer 1. Thus, a decorative sheet having the base material sheet 4, the pattern layer 3, the transparent resin layer 2, and the surface protective layer 1 in this order can also be manufactured.

[0094] The pattern layer 3 is formed by applying ink used for forming the pattern layer 3 onto the transparent resin layer 2 or the base material sheet 4 to provide a desired colored layer and pattern layer. The application of the ink can be performed by a known method such as the gravure printing method, bar coating method, roll coating method, reverse roll coating method, comma coating method, etc., preferably the gravure printing method.

[0095] In the formation of the surface protective layer 1, the curable resin composition is preferably applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., more preferably by gravure coating, so that the thickness after curing becomes a predetermined thickness.

[0096] When an ionizing radiation resin composition is used for the formation of the surface protective layer 1, the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as electron beams or ultraviolet rays to be cured to form the surface protective layer 1. Here, when electron beams are used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, 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 crosslinking density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). There is no particular limitation on the electron beam source, and for example, various electron beam accelerators such as a Cockcroft-Walton type, a Van de Graaff type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used.

[0097] When ultraviolet rays are used as the above ionizing radiation, those emitting ultraviolet rays with a wavelength of 190 to 380 nm are radiated. There is no particular limitation on the ultraviolet ray source, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

[0098] When a thermosetting resin composition is used for the formation of the surface protective layer 1, heat treatment according to the resin composition used may be performed to cure it to form the surface protective layer 1.

[0099] When providing the above primer layer, the resin composition for forming the primer layer can be formed by applying it by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma coating method, etc.

[0100] Next, recesses having the above-described shape are formed in the surface protective layer 1. In consideration of workability, it is preferable to employ embossing for forming the recesses. The embossing may be carried out by a usual method using a known sheet-fed or rotary embossing machine.

[0101] The decorative sheet of the present invention having the above-described configuration appropriately imparts hardness to the transparent resin layer and the surface protective layer, and has a predetermined recess on the surface on the side having the surface protective layer, so that it has a sufficient tactile sensation, excellent scratch resistance, abrasion resistance, and stain resistance, and productivity is not reduced.

[0102] A decorative material in which the decorative sheet of the present invention and a base material are laminated is also one of the present inventions.

[0103] <Base material> Examples of the base material 20 include at least one of wood-based materials such as medium-density wood fiberboard, high-density wood fiberboard, particle board, softwood plywood, hardwood plywood, early-growth tree plywood, cork sheet, and cork-containing composite base material, and thermoplastic resin plates (resin plates mainly composed of polyvinyl chloride resin, polypropylene resin, polyethylene resin, acrylic resin, ABS resin, etc., or those obtained by foaming them).

[0104] Here, examples of softwood include linden pine, tang pine, Japanese larch, cedar, cypress, pine, sequoia, hemlock, etc. Examples of hardwood include lauan, Chinese fir, oak, elm, beech, oak, melianthus, etc. Examples of early-growth trees include poplar, falcata, acacia, camerere, eucalyptus, terminalia, etc.

[0105] When using wood-based plywood such as softwood plywood, hardwood plywood, and early-growth tree plywood, the number of plies (ply number) of the wood veneer is not limited, but usually 3 to 7 plies are preferable, and 5 to 7 plies are more preferable. Also, the adhesive used in manufacturing the wood-based plywood is not limited, and known woodworking adhesives can be widely used.

[0106] Examples of the above-mentioned 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. Further, examples of the thermosetting adhesive include adhesives such as melamine-based, phenol-based, and urea-based (such as vinyl acetate-urea-based) adhesives.

[0107] The thickness of the base material 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.

[0108] The lamination method for laminating the decorative sheet 10 of the present invention and the base material 20 is not limited, and for example, a method of adhering each with an adhesive can be adopted. The above-mentioned adhesive may be appropriately selected from known adhesives. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, urethane-based reactive hot melt (hereinafter referred to as "PUR-based adhesive"), etc., reactive hot melt adhesives, and butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. are included. These adhesives can be used alone or in combination of two or more.

Examples

[0109] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by this example.

[0110] (Example 1) A colored polypropylene film with a thickness of 60 μm was prepared as a base material sheet, and a pattern layer (5 μm thick) was laminated on one surface thereof using a gravure printing machine. On the other hand, an olefin-based film (random polypropylene, clear) with a thickness of 80 μm and an indentation hardness of 50 MPa was prepared as a transparent resin layer, and it was bonded to the above-mentioned pattern layer through a 2 μm two-component curable adhesive made of urethane resin. After applying a curable resin composition (a polyfunctional urethane acrylate oligomer) by gravure coating on the surface of the above-mentioned transparent resin layer and then irradiating it with ionizing radiation to cure it, a surface protective layer with a thickness of 13 μm and an indentation hardness of 160 MPa was provided. Thereafter, embossing was performed by thermocompression from the side where the surface protective layer was formed, thereby forming an uneven pattern (recessed portion) of a wood grain conduit pattern (grooved shape). The density of the formed recessed portions was 27%, the average depth of the recessed portions was 75 μm, the maximum depth of the recessed portions was 80 μm, and the average width of the recessed portions was 510 μm. Also, the total thickness of the obtained decorative sheet was 160 μm.

[0111] (Example 2) A decorative sheet was produced in the same manner as in Example 1, except that grooved recessed portions were provided such that the density of the recessed portions was 35%, the average depth of the recessed portions was 60 μm, the maximum depth of the recessed portions was 80 μm, and the average width of the recessed portions was 510 μm.

[0112] (Example 3) A decorative sheet was produced in the same manner as in Example 1, except that grooved recessed portions were provided such that the density of the recessed portions was 35%, the average depth of the recessed portions was 90 μm, the maximum depth of the recessed portions was 110 μm, and the average width of the recessed portions was 510 μm.

[0113] (Example 4) A decorative sheet was produced in the same manner as in Example 1, except that grooved recessed portions were provided such that the density of the recessed portions was 40%, the average depth of the recessed portions was 87 μm, the maximum depth of the recessed portions was 120 μm, and the average width of the recessed portions was 440 μm.

[0114] (Example 5) A decorative sheet was produced in the same manner as in Example 1, except that the indentation hardness of the surface protective layer was changed to 250 MPa and grooved recessed portions were provided such that the density of the recessed portions was 35%, the average depth of the recessed portions was 90 μm, the maximum depth of the recessed portions was 110 μm, and the average width of the recessed portions was 500 μm.

[0115] (Example 6) A decorative sheet was produced in the same manner as in Example 1, except that the thickness of the transparent resin layer was changed to 60 μm, and groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 500 μm.

[0116] (Example 7) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 20%, the average depth of the recesses was 60 μm, the maximum depth of the recesses was 80 μm, and the average width of the recesses was 510 μm.

[0117] (Example 8) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 40 μm, the maximum depth of the recesses was 60 μm, and the average width of the recesses was 350 μm.

[0118] (Example 9) A decorative sheet was produced in the same manner as in Example 1, except that the indentation hardness of the surface protective layer was changed to 100 MPa, and groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 510 μm.

[0119] (Example 10) A decorative sheet was produced in the same manner as in Example 1, except that the indentation hardness of the transparent resin layer was changed to 40 MPa, and groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 510 μm.

[0120] (Example 11) A decorative sheet was produced in the same manner as in Example 1, except that 3.0 parts by mass of a phosphate glass silver-supported compound (manufactured by Koa Glass Co., Ltd.) was added to 100 parts by mass of the resin component in the curable resin composition (polyfunctional urethane acrylate oligomer) for forming the surface protective layer.

[0121] (Comparative Example 1) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 5%, the average depth of the recesses was 15 μm, the maximum depth of the recesses was 20 μm, and the average width of the recesses was 300 μm.

[0122] (Comparative Example 2) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 400 μm.

[0123] (Comparative Example 3) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 20%, the average depth of the recesses was 75 μm, the maximum depth of the recesses was 90 μm, and the average width of the recesses was 350 μm.

[0124] (Comparative Example 4) The transparent resin layer was changed to a thickness of 40 μm, and a decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 510 μm.

[0125] (Comparative Example 5) The indentation hardness of the transparent resin layer was changed to 30 MPa, and a decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 510 μm.

[0126] (Comparative Example 6) The indentation hardness of the surface protective layer was changed to 90 MPa, and a decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 35%, the average depth of the recesses was 90 μm, the maximum depth of the recesses was 110 μm, and the average width of the recesses was 510 μm.

[0127] (Comparative Example 7) A decorative sheet was produced in the same manner as in Example 1, except that groove-shaped recesses were provided such that the density of the recesses was 40%, the average depth of the recesses was 27 μm, the maximum depth of the recesses was 40 μm, and the average width of the recesses was 500 μm.

[0128] <Evaluation method> (Indentation hardness) The indentation hardness of the surface protective layer and the transparent resin layer was measured by the method described in the main text of the specification.

[0129] (Average width, average depth, and maximum depth of the recesses) The average width, average depth, and maximum depth of the recesses were measured by the method described in the main text of the specification.

[0130] The scratch resistance, abrasion resistance, stain resistance, productivity, and touch feeling were evaluated by the following methods. In all evaluations, those with “+ / -” or higher were considered qualified in the comprehensive evaluation.

[0131] (1) Scratch resistance For the decorative sheets produced in the examples and comparative examples, tests were conducted using a Hoffman scratch tester (manufactured by BYK-GARDNER). Specifically, a scratch blade (a cylindrical blade with a diameter of φ7 mm) was set to contact the surface of the decorative sheet of the decorative material at an angle of 45°, and the tester was moved on the decorative material. The load (weight) was gradually increased by 100 g each time, and the test was repeated until scratches, indentations, etc. occurred on the surface of the decorative sheet, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 1. +: The initial load for damage is 300 g or more + / -: The initial load for damage is 100 g or more and less than 300 g -: The initial load for damage is less than 100 g

[0132] (2) Stain resistance For the decorative sheets produced in the examples and comparative examples, after red crayon was applied three times in a range of 1 cm × 7 cm on the surface and left for 15 minutes, a tissue was dipped in ethanol and wiped off, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 1. +: The red crayon was completely wiped off + / -: The red crayon could not be completely wiped off in part -: The red crayon could not be wiped off for most part

[0133] (3) Abrasion resistance For the cosmetic sheets prepared in the examples and comparative examples, the abrasion resistance test specified in the Japanese Agricultural and Forestry Standards of JAS flooring was carried out to confirm the number of rotations until the pattern began to disappear, and the evaluation was made according to the following criteria. The evaluation results are shown in Table 1 +: There was no disappearance of the pattern even after 1000 consecutive rotations + / -: The disappearance of the pattern occurred after 500 or more consecutive rotations and less than 1000 rotations -: The disappearance of the pattern occurred after less than 500 consecutive rotations

[0134] (4) Productivity of the cosmetic sheet In the examples and comparative examples, after forming the surface protective layer, the production state when embossing was carried out under the conditions of a sheet temperature of 160 °C and a pressure of 40 kg / cm 2 was confirmed, and the evaluation was made according to the following criteria. The evaluation results are shown in Table 1 +: Production was possible without problems + / -: Cracks occurred partially at the bottom of the concave part, but production was possible -: Production was impossible due to sheet breakage, etc

[0135] (5) Tactile sensation Ten adult men and women in their 20s to 40s confirmed the unevenness on the surface of the cosmetic sheets prepared in the examples and comparative examples by touch, and the evaluation was made according to the following criteria. The evaluation results are shown in Table 1 ++: All 10 people were able to feel the unevenness +: 8 or 9 people were able to feel the unevenness + / -: 4 or more and less than 8 people were able to feel the unevenness -: 3 or fewer people were able to feel the unevenness

[0136]

Table 1

[0137] In the decorative sheet of the example in which the indentation hardness of the transparent resin layer and the surface protective layer is within a predetermined range and the density and shape of the concave portions are within a predetermined range, all evaluations of scratch resistance, abrasion resistance, stain resistance, productivity, and touch feeling were "+ / -" or more, and the comprehensive evaluation was a pass. On the other hand, in the decorative sheet of Comparative Example 1 in which the density of the concave portions was less than 20% and the average depth of the concave portions was less than 40 μm, the touch feeling was insufficient. Also, in the decorative sheets of Comparative Examples 2 and 3 in which the ratio of the average width to the average depth of the concave portions (average width / average depth) was less than 5, the stain resistance was insufficient. Also, in the decorative sheet of Comparative Example 4 in which the maximum depth of the concave portions exceeded 80% with respect to the total thickness of the decorative sheet, the productivity of the sheet decreased. Also, in the decorative sheet of Comparative Example 5 in which the indentation hardness of the transparent resin layer was less than 40 MPa, the scratch resistance was insufficient. Also, in the decorative sheet of Comparative Example 6 in which the indentation hardness of the surface protective layer was less than 100 MPa, the scratch resistance was insufficient. Also, Comparative Example 7 in which the average depth of the concave portions was less than 40 μm had a deeper depth of the concave portions compared to Comparative Example 1, but the touch feeling was insufficient.

[0138] (6) Antiviral test Regarding the decorative sheet produced in Example 11, a test was carried out by a method compliant with the antiviral test method (ISO21702), the antiviral activity value against influenza virus was calculated, and an antiviral activity value of 2.0 or more was evaluated as a pass. As a result, in the decorative sheet produced in Example 11, the antiviral activity on the surface was 3.1, and it was confirmed that it had antiviral properties.

Industrial applicability

[0139] According to the present invention, it is possible to obtain a decorative sheet having sufficient touch feeling, excellent scratch resistance, abrasion resistance, and stain resistance, and not causing a decrease in productivity, and a decorative material using the decorative sheet.

Explanation of symbols

[0140] 1 Surface protection layer 2 Transparent resin layer 3 Pattern layer 4 Base sheet 10 Decorative sheet 20 Base material 30 Measurement sample 31 Vickers indenter 32 Direction of applying load 40 Sample 41 Measurement region 100 Decorative material

Claims

1. A decorative sheet having at least a pattern layer, a transparent resin layer, and a surface protection layer in this order on a base material sheet, The decorative sheet has a plurality of groove-shaped recesses on the surface on the side having the surface protection layer, The indentation hardness of the transparent resin layer is 40 MPa or more, The indentation hardness of the surface protection layer is 100 MPa or more, The recess satisfies the following conditions (A) to (E) A decorative sheet characterized by this. (A) The density of the plurality of groove-shaped recesses when the decorative sheet is viewed in plan is 20% or more and 45% or less. (B) The average depth of the plurality of groove-shaped recesses is 40 μm or more. (C) The ratio of the average width to the average depth (average width / average depth) of the plurality of groove-shaped recesses is 5 or more. (D) The maximum depth of the plurality of groove-shaped recesses is 80% or less of the total thickness of the decorative sheet. (E) The average width of the plurality of groove-shaped recesses is 300 μm or more and 1000 μm or less. However, the average width and the average depth are measured by the following method. (Measurement method of average width) Arbitrarily select 10 measurement regions on the surface on the side having the surface protection layer. In the measurement region, select three groove-shaped recesses, select the place where the width is the largest, and measure its length. The value obtained by averaging the measured values of the three points is taken as the width of the recess in one measurement region. The average value of the values obtained in the 10 measurement regions is taken as the average width. (Measurement method of average depth) Arbitrarily select 10 measurement regions on the surface on the side having the surface protection layer. In the measurement region, select three groove-shaped recesses, and measure the maximum value of the distance parallel to the thickness direction from the bottom of the recess to the flat surface portion of the surface. Among the measured numerical values of the three points, the maximum value shall be taken as the maximum depth of the groove-shaped recess in the measurement area of 1. The average value of the numerical values obtained in the ten measurement areas shall be taken as the average depth.

2. The cosmetic sheet according to claim 1, wherein the density of the plurality of groove-shaped recesses is 35% or less.

3. The cosmetic sheet according to claim 1 or 2, wherein the average depth of the plurality of groove-shaped recesses is 60 μm or more.

4. The cosmetic sheet according to any one of claims 1 to 3, wherein the ratio of the average width to the average depth of the plurality of groove-shaped recesses (average width / average depth) is 6 or more.

5. The cosmetic sheet according to any one of claims 1 to 4, wherein the surface protective layer contains an antiviral agent.

6. The cosmetic sheet according to any one of claims 1 to 5, wherein the maximum depth of the plurality of groove-shaped recesses is 65% or less with respect to the total thickness of the cosmetic sheet.

7. A decorative material, characterized in that the cosmetic sheet according to any one of claims 1 to 6 and a base material are laminated.

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