Makeup sheets and makeup boards

Abstract

The present invention provides a cosmetic sheet having excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, as well as excellent design properties. The present invention provides a cosmetic sheet having a surface protection layer on the outermost surface, wherein (1) the Martens hardness of the surface protection layer is 30 to 170 N / mm², and the Martens hardness is a value obtained by measuring the Martens hardness of the cross-section by pressing a diamond indenter into a position avoiding the fine particles when the surface protection layer contains fine particles, (2) the surface protection layer has irregularities, and the irregularities have an embossed shape of sand grain, wood grain, bark grain, stone grain, or leather grain, and the average spacing (Sm) of the irregularities is 180 μm to 950 μm, (3) the maximum height (Rz) of the surface protection layer is 10 to 45 μm, and (4) the area ratio of the portion from the surface to a depth of 30 μm is 40% or more.

Description

Technology Field

[0001] The present invention relates to cosmetic sheets and cosmetic plates. Background Technology

[0002] Decorative sheets are applied to surfaces such as wooden boards and plastic boards for the purpose of surface protection and decoration. Additionally, the decorative panels obtained in this way are used in various building materials, furniture, and the like.

[0003] Conventional decorative sheets generally have a smooth surface. Consequently, when used as flooring for surfaces such as flooring or stairs, people may slip and fall when walking on them.

[0004] Therefore, a floor-mounted cosmetic sheet is proposed in which a plurality of convex portions are formed on the surface for the purpose of providing anti-slip properties to the surface of the cosmetic sheet, the cross-sectional shape in the height direction of the convex portions is trapezoidal or awl-shaped, and when viewed in a planar view, the shape of the convex portions is polygonal and has a specific range of sizes (Patent Document 1).

[0005] However, the flooring material of Patent Document 1 has a problem in that it does not have sufficient anti-slip properties. In addition, cosmetic sheets with fillers added to the surface protection layer or cosmetic sheets with embossing processing have a problem in that when used, the surface of the filler is worn away, and the specific surface irregular shape is lost, causing the anti-slip properties to gradually decrease.

[0006] Furthermore, since cosmetic sheets are applied to surfaces such as wooden or plastic boards, they may come into contact with objects. For this reason, impact resistance is required for cosmetic sheets. Additionally, stain resistance is required as it must be easy to wipe off contaminants that adhere to the surface.

[0007] Moreover, since decorative sheets are attached to the surface of articles for decorative purposes, they are required to have excellent design quality. The floor decorative sheet described in Patent Document 1 has a problem in that its design quality is inferior because the convex shape is polygonal, so it can be clearly identified as an industrial plastic product.

[0008] Therefore, there is a need to develop a cosmetic sheet that has excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, as well as excellent design properties. Prior art literature

[0009] [Patent Document 1] Japanese Patent Publication No. 6606901 The problem to be solved

[0010] The main purpose of the present invention is to provide a cosmetic sheet that has excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, and also has excellent design properties. means of solving the problem

[0011] As a result of repeated research, the inventors discovered that the above objective can be achieved by a cosmetic sheet having a surface protection layer on its outermost surface, provided that the surface of the surface protection layer satisfies specific conditions, and thus completed the present invention.

[0012] That is, the present invention relates to the following cosmetic sheets and cosmetic plates.

[0013] 1. A cosmetic sheet having a surface protection layer on its outermost surface,

[0014] (1) The Martens hardness of the surface protection layer is 30 to 170 N / mm², and the Martens hardness is a value obtained by measuring the Martens hardness of the cross-section by pressing a diamond indenter into a location avoiding the fine particles when the surface protection layer contains fine particles, and

[0015] (2) The surface protective layer has irregularities, and the irregularities have an embossed shape of sand grain, wood grain, bark grain, stone grain, or leather grain, and the average spacing (Sm) of the irregularities is 180 μm to 950 μm, and

[0016] (3) The maximum height (Rz) of the above surface protection layer is 10 to 45 μm, and

[0017] (4) A cosmetic sheet characterized in that the surface protection layer has an area ratio of 40% or more of the portion from the surface to a depth of 30 μm.

[0018] 2. The cosmetic sheet described in Claim 1, having a Martens hardness of 70 to 150 N / mm².

[0019] 3. A cosmetic sheet as described in claim 1 or 2, having an Rz of 10 to 19 μm.

[0020] 4. A cosmetic sheet described in any one of claims 1 to 3, wherein the above Sm is 450 to 750 μm.

[0021] 5. The above surface protective layer is a cosmetic sheet described in any one of claims 1 to 4, wherein the area ratio of the portion higher than a depth of 30 μm from the surface is 50% to 90%.

[0022] 6. The above surface protective layer is a cosmetic sheet described in any one of claims 1 to 5, wherein the area ratio of the portion higher than a depth of 30 μm from the surface is 60% to 85%.

[0023] 7. A cosmetic sheet described in any one of claims 1 to 6, wherein the surface protective layer contains an ionizing radiation-curing resin.

[0024] 8. A cosmetic sheet described in any one of claims 1 to 7, wherein the thickness of the surface protective layer is 10 to 40 μm.

[0025] 9. A cosmetic sheet described in any one of claims 1 to 8, wherein the surface protective layer contains at least one selected from the group consisting of antibacterial agents, antiviral agents, and anti-allergen agents.

[0026] 10. A cosmetic sheet described in any one of claims 1 to 9, having a patterned layer, a transparent resin layer, and the surface protection layer in sequence on a substrate sheet.

[0027] 11. A cosmetic sheet described in any one of claims 1 to 9, having a patterned layer, a transparent resin layer, and a surface protection layer in sequence on a substrate sheet, and having at least a backer layer laminated on the back side of the substrate sheet.

[0028] 12. A cosmetic plate having a cosmetic sheet described in any one of claims 1 to 11 on a substrate.

[0029] 13. The decorative board described in claim 12, which is a wood veneer, wood plywood, wood fiberboard, or particle board. Effects of the invention

[0030] The decorative sheet of the present invention has excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, and also has excellent design properties. Therefore, a decorative board laminated with the decorative sheet of the present invention can be used in various building materials, furniture, etc. Brief explanation of the drawing

[0031] FIG. 1 is a schematic diagram (cross-sectional view) of a cosmetic sheet of the present invention. FIG. 2 is a drawing illustrating a diamond indenter (a) used for measuring Martens hardness in the present specification, a schematic diagram of the indentation operation (b), and an example of the indentation load and displacement (c). Figure 3 is a drawing showing the measured cross-sectional curve of the cosmetic sheet produced in Example 4. Figure 4 is a drawing showing the area where the measurement cross-sectional curve was measured in Example 4. Figure 5 is a diagram illustrating the measurement results of the volume area 1 of the cosmetic sheet produced in Example 4. Figure 6 is a diagram illustrating the measurement results of the volume area 2 of the cosmetic sheet produced in Example 4. Figure 7 is a drawing illustrating the measured cross-sectional curve of the cosmetic sheet produced in Example 7. Figure 8 is a drawing showing the area where the measurement cross-sectional curve was measured in Example 7. Figure 9 is a diagram illustrating the measurement results of the volume area 1 of the cosmetic sheet produced in Example 7. Figure 10 is a diagram showing the measurement results of the volumetric area 2 of the cosmetic sheet produced in Example 7. Figure 11 is a drawing showing the measured cross-sectional curve of the cosmetic sheet produced in Comparative Example 7. Figure 12 is a drawing showing the area where the measurement cross-sectional curve was measured in Comparative Example 7. Figure 13 is a drawing showing the measurement results of the volume area 1 of the cosmetic sheet produced in Comparative Example 7. Figure 14 is a drawing showing the measurement results of the volume area 2 of the cosmetic sheet produced in Comparative Example 7. Specific details for implementing the invention

[0032] 1. Makeup sheet

[0033] The cosmetic sheet of the present invention is a cosmetic sheet having a surface protection layer on its outermost surface,

[0034] (1) The Martens hardness of the surface protection layer is 30 to 170 N / mm², and the Martens hardness is a value obtained by measuring the Martens hardness of the cross-section by pressing a diamond indenter into a location avoiding the fine particles when the surface protection layer contains fine particles, and

[0035] (2) The surface protective layer has irregularities, and the irregularities have an embossed shape of sand grain, wood grain, bark grain, stone grain, or leather grain, and the average spacing (Sm) of the irregularities is 180 μm to 950 μm, and

[0036] (3) The maximum height (Rz) of the surface protection layer is 10 to 45 μm, and

[0037] (4) The above surface protection layer is a cosmetic sheet characterized by having an area ratio of 40% or more of the portion from the surface to a depth of 30 μm.

[0038] Since the cosmetic sheet of the present invention possesses the above characteristics, it exhibits excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, and also has excellent aesthetic appeal. Therefore, the floor cosmetic sheet of the present invention can be suitably used for floors.

[0039] The cosmetic sheet of the present invention will be described in detail below. Furthermore, in the cosmetic sheet of the present invention, the surface refers to the so-called "outer surface," which is the side opposite to the surface in contact with the substrate when the cosmetic sheet of the present invention is laminated and used with the substrate, etc., and is the side that is visible after lamination. Additionally, in this specification, regarding the cosmetic sheet of the present invention, the direction of the above surface may be referred to as the "outer surface" or "upper," and the opposite side may be referred to as the "rear surface" or "lower." Furthermore, in the following description, the lower limit and upper limit of a numerical range indicated by "~" mean "greater than or equal to or less than" (for example, if α to β, it means α greater than or equal to or less than β).

[0040] In addition, the layer thickness in this specification is a value measured in a region of the cosmetic sheet where there are no irregular shapes, such as embossing or protrusions of fine particle heads.

[0041] (Layer composition of the cosmetic sheet of the present invention)

[0042] The cosmetic sheet of the present invention may have the surface protection layer on its outermost surface, and the specific composition may be appropriately set according to the use of the cosmetic sheet, etc. For example, a cosmetic sheet having any one of a patterned layer, a transparent adhesive layer, a transparent resin layer, and a primer layer on a substrate sheet, and having a surface protection layer on its outermost surface may be provided.

[0043] Hereinafter, regarding the cosmetic sheet of the present invention, a cosmetic sheet having a patterned layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and the surface protection layer in sequence on a substrate sheet will be described in detail as a representative example.

[0044] (Recording Sheet)

[0045] On the surface (outer surface) of the substrate sheet, pattern-shaped layers, etc., are sequentially laminated.

[0046] For example, a sheet (film) formed by a thermoplastic resin is suitable as the base sheet. Specifically, examples include olefin-based resins such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, ethylene-(meth)acrylic acid copolymer, and ethylene-(meth)acrylic acid ester copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, ionomer, acrylic acid ester-based polymer, and methacrylic acid ester-based polymer. The base sheet is formed by using these resins alone or in combination of two or more types.

[0047] Additionally, in this specification, “(meth)acrylic acid” means acrylic acid and / or methacrylic acid, and the same applies to other parts described as (meth).

[0048] The base sheet may be colored. In this case, the thermoplastic resin described above may be colored by adding a coloring agent (pigment or dye). As coloring agents, various dyes may be used in addition to inorganic pigments such as titanium dioxide, carbon black, and iron oxide, and organic pigments such as phthalocyanine blue. One or more of these may be selected from known or commercially available ones. In addition, the amount of coloring agent added may be appropriately set according to the desired color tone, etc.

[0049] The base sheet may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers, as needed.

[0050] The thickness of the substrate sheet can be appropriately set according to the purpose and method of use of the final product, but generally, 20 to 300 μm is preferred.

[0051] If necessary, the substrate sheet may be subjected to corona discharge treatment on its surface (outer surface) to improve the adhesion of the ink forming the pattern layer. The method and conditions of the corona discharge treatment may be carried out according to known methods. Additionally, if necessary, corona discharge treatment may be performed on the back side of the substrate sheet or a back side primer layer may be formed.

[0052] (Pattern-shaped layer)

[0053] The cosmetic sheet of the present invention may have a patterned layer.

[0054] The pattern layer imparts a desired pattern (design) to the decorative sheet, and the types of patterns are not limited. Examples include wood grain, laser pattern, stone grain, sand grain, tile attachment pattern, bricklaying pattern, fabric grain pattern, geometric shapes, letters, symbols, abstract shapes, etc.

[0055] The method of forming the patterned layer is not particularly limited; for example, it may be formed on the surface of a substrate sheet by a printing method using an ink obtained by dissolving (or dispersing) a known coloring agent (dye or pigment) together with a binder resin in a solvent (or dispersion medium). For the ink, an aqueous composition may also be used from the perspective of reducing VOCs in the cosmetic sheet.

[0056] Examples of coloring agents include inorganic pigments such as carbon black, titanium white, zinc oxide, Bengala, indigo, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth chloride oxide; fluorescent pigments; and phosphorescent pigments. These coloring agents may be used alone or in a mixture of two or more types. These coloring agents may also be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants, etc.

[0057] As a binder resin, in addition to hydrophilically treated polyester-based urethane resin, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative, alcohol adduct of styrene-maleic anhydride copolymer, cellulose-based resin, etc., may also be used. More specifically, examples include polyacrylamide-based resin, poly(meth)acrylic acid-based resin, polyethylene oxide-based resin, polyN-vinylpyrrolidone-based resin, water-soluble polyester-based resin, water-soluble polyamide-based resin, water-soluble amino-based resin, water-soluble phenol-based resin, and other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides; etc. may also be used. In addition, modified forms such as natural rubber, synthetic rubber, polyvinyl acetate resin, (meth)acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc., or mixtures of the above natural rubber, etc., and other resins may also be used. The above binder resin may be used alone or in combination of two or more types.

[0058] Examples of solvents (or dispersion media) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in a mixture of two or more.

[0059] Printing methods used to form a pattern layer include, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Additionally, when forming a full-surface solid pattern layer, various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating may be used. Furthermore, handwriting, ink flow, photography, transfer, laser beam lithography, electron beam lithography, partial deposition of metals, etching, etc., may be used, or they may be used in combination with other forming methods.

[0060] The thickness of the pattern layer is not specifically limited and can be appropriately set according to product characteristics, but the layer thickness is about 0.1 to 10 μm.

[0061] (Colored opacity layer)

[0062] In the cosmetic sheet of the present invention, a coloring concealing layer may be additionally formed between the base sheet and the pattern shape layer.

[0063] The colored concealing layer can conceal the base color of the substrate when the cosmetic sheet and the substrate are bonded, and typically, it can be formed to cover the substrate sheet.

[0064] The printing method known above may be used to form the colored opacity layer. In addition, the ink used to form the pattern layer may be used as is.

[0065] The coating amount is preferably in the range of 2 to 30 g / m². The thickness of the colored opacity layer is typically about 0.1 to 20 μm, preferably about 1 to 10 μm.

[0066] (Adhesive layer)

[0067] To enhance the adhesion between the transparent resin layer and the pattern layer described below, an adhesive layer may be formed on the pattern layer. The adhesive layer is preferably a transparent adhesive layer, and the transparent adhesive layer may include any of the following: colorless transparent, colored transparent, translucent, etc.

[0068] The adhesive is not particularly limited, and any adhesive known in the field of cosmetic sheets may be used.

[0069] Adhesives known in the field of cosmetic sheets include, for example, thermoplastic resins such as polyamide resin, acrylic resin, and vinyl acetate resin, and thermosetting resins such as urethane resin. These adhesives are used individually or in combination of two or more types. In addition, two-component curing polyurethane resins or polyester resins using isocyanate as a curing agent may also be applied.

[0070] The printing method known above can be used to form the transparent adhesive layer.

[0071] The thickness of the transparent adhesive layer is not particularly limited, but the thickness after drying is about 0.1 to 30 μm, preferably about 1 to 20 μm.

[0072] (Transparent resin layer)

[0073] The floor cosmetic sheet of the present invention may have a transparent resin layer.

[0074] The transparent resin layer is not particularly limited as long as it is transparent, and includes any of the following: colorless transparent, colored transparent, translucent, etc. As resins constituting the transparent resin layer, examples include polypropylene such as polyethylene, ethylene-α-olefin copolymer, homopolypropylene, and random polypropylene; polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product; ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, and olefin elastomer; olefin resins such as polyethylene terephthalate, polybutylene terephthalate, polyamide, ionomer, acrylic acid ester-based polymer, methacrylic acid ester-based polymer, polycarbonate, cellulose australacetate, etc. These resins may be used alone or in combination of two or more types.

[0075] It is preferable that the transparent resin layer is a transparent thermoplastic resin layer, more preferable that it includes an olefin-based resin represented by polypropylene resin or polyethylene resin, and even more preferable that the resin constituting the transparent resin layer is the said olefin-based resin or ionomer-based resin.

[0076] In addition, the transparent resin layer may be colored as long as it is transparent, but it is particularly preferable not to incorporate a coloring agent.

[0077] The thickness of the transparent resin layer is typically about 20 to 200 μm, but it may exceed the above range depending on the use of the flooring decorative sheet, etc.

[0078] (Primer layer)

[0079] A primer layer may be formed on the transparent resin layer. The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of primer agents include urethane resin-based primer agents containing, for instance, acrylic-modified urethane resin (acrylurethane-based resin), primer agents containing urethane-cellulose-based resin (e.g., a resin formed by adding hexamethylene diisocyanate to a mixture of urethane and nitrocellulose), and resin-based primer agents containing block copolymers of acrylic and urethane. Additives may be incorporated into the primer agent as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, light stabilizers, etc. The amount of additives incorporated can be appropriately set according to the product characteristics.

[0080] The amount of primer applied is not particularly limited, but is typically 0.1 to 100 g / m², preferably 0.1 to 50 g / m².

[0081] The thickness of the primer layer is not particularly limited, but is typically 0.01 to 10 μm, preferably 0.1 to 1 μm.

[0082] (Surface protection layer)

[0083] The cosmetic sheet of the present invention has a surface protection layer on its outermost surface having a Martens hardness (hardness) of 30 to 170 N / mm². The preferred Martens hardness of the surface protection layer is 70 to 150 N / mm².

[0084] In addition, the Martens hardness in this specification was measured using a PICODENTOR HM-500 (manufactured by Fisher Instruments) Martens hardness measuring device in accordance with ISO 14577. The indentation conditions were as shown in FIG. 2(c) at room temperature (laboratory environment temperature), first applying a load of 0 to 5 mN for 10 seconds, then maintaining a load of 5 mN for 5 seconds, and finally removing the load from 5 to 0 mN for 10 seconds. In addition, in this specification, the Martens hardness of the cross-section of the surface protection layer was measured to avoid the influence of the hardness of layers other than the surface protection layer. At this time, a cosmetic sheet was embedded in a resin (such as a cold-curing type epoxy two-component curing resin or a UV-curable resin), and after being left at room temperature for more than 24 hours to cure, the cured embedded sample was cut and mechanically polished to expose the cross-section of the surface protective layer, and the Martens hardness of the cross-section was measured by pressing a diamond indenter into the cross-section (in cases where fine particles such as fillers are included in the layer, at a location avoiding the fine particles).

[0085] The martens hardness of the surface protection layer can be appropriately set by 1) mixing multiple resin components, 2) adding an elastomer to the resin, etc. For example, when using the urethane acrylate described below as the resin component constituting the surface protection layer, the desired martens hardness can be obtained by appropriately mixing bifunctional urethane acrylate and hexafunctional urethane acrylate, or by using only trifunctional urethane acrylate with a molecular weight of about 1500. Furthermore, the term bifunctional urethane acrylate here refers to a urethane acrylate having two radical polymerizable acryloyl groups within one molecule. Likewise, regarding trifunctional urethane acrylate and hexafunctional urethane acrylate, they refer to urethane acrylates having three and six radical polymerizable acryloyl groups within one molecule, respectively.

[0086] In addition, the cosmetic sheet of the present invention has a specific uneven shape on its surface. In the cosmetic sheet of the present invention, the unevenness forming the said uneven shape is an embossed shape of sand grain, wood grain, tree bark grain, stone grain, or leather grain. By the unevenness being an embossed shape, the cosmetic sheet of the present invention can be made into a cosmetic sheet with excellent anti-slip properties, anti-slip durability, impact resistance, and stain resistance, as well as excellent decorative properties.

[0087] The average spacing (Sm) of the above irregularities is 180 μm to 950 μm. If Sm is less than 180 μm, the aesthetic appeal is inferior, and if it exceeds 950 μm, the anti-slip performance is inferior. Sm is preferably 450 to 750 μm.

[0088] The above Sm is an indicator representing the spacing of irregularities in the surface protection layer. It is calculated by drawing a reference length (L) from the roughness curve of the surface protection layer in the direction of the average line, determining the sum of the lengths of the average lines corresponding to one peak and one adjacent valley, and representing the average value of the said sum. If Sm is small, the surface texture is fine (the irregularities are dense).

[0089] In addition, the maximum height (Rz) of the surface protective layer is 10 to 45 μm. If Rz is less than 10 μm, the aesthetic quality is inferior, and if it exceeds 45 μm, the stain resistance is inferior. Rz is preferably 10 to 30 μm, and more preferably 10 to 19 μm.

[0090] The above Rz is an indicator representing the maximum height of the surface protection layer, and represents the sum of the height (Ha) from the average line of the surface protection layer drawn out from the roughness curve in the direction of the average line and the depth (Hb) from the highest mountain peak to the lowest valley bottom (Rz=Ha+Hb).

[0091] The above Sm conforms to the JIS B0601 (1994) and Rz conforms to the JIS B0601 (2001) surface roughness standards.

[0092] The above-mentioned Sm and Rz can both be obtained by measuring surface roughness. Surface roughness can be measured using a surface roughness shape measuring instrument, such as the SharpComm 120A (manufactured by Tokyo Seimitsu Co., Ltd.).

[0093] In the cosmetic sheet of the present invention, the surface protective layer has an area ratio of 40% or more for the portion extending from the surface to a depth of 30 μm. If the ratio is less than 40%, the anti-slip properties of the cosmetic sheet are inferior. The ratio is preferably 50% to 90%, and more preferably 60% to 85%. If the upper limit of the ratio is within the above range, the aesthetic properties of the cosmetic sheet are further improved. Furthermore, the area of ​​the portion extending from the surface to a depth of 30 μm is the area of ​​the portion that comes into contact with the foot when walking on the surface of the cosmetic sheet, and is also referred to as the "contact area." The ratio is measured by the following measurement method.

[0094] [Ratio of the area (contact area) of the portion from the surface to a depth of 30 µm]

[0095] The ratio of the area (contact area) of the portion from the surface of the cosmetic sheet to a depth of 30 μm is measured using a laser microscope VK-X1000 (manufactured by Giensuga Bushiki Kaisha). Specifically, under the condition of a lens magnification of 50x, the total volume area 1 from the surface of the cosmetic sheet is measured for an area of ​​1 cm². Subsequently, the volume area 2 from the surface to a depth of 30 μm is measured, and the contact area ratio is calculated based on the following formula.

[0096] (Contact Area Ratio (%)) = (Volume Area 2 / Volume Area 1) × 100

[0097] Here, volume area 1 is the area of ​​all surfaces forming the surface of the cosmetic sheet, such as the smooth surface area of ​​the cosmetic sheet, the uneven wall surface, and the bottom surface. Additionally, volume area 2 is the area obtained by measuring the area of ​​the surface from the surface to a depth of 30 μm using the laser microscope VK-X1000, and is the contact area described above.

[0098] FIGS. 3 to 14 illustrate examples of measuring the area ratio of the portion of the surface protection layer from the surface to a depth of 30 μm in Example 4, Example 7, and Comparative Example 7, which will be described later. Specifically, FIG. 3 is a measured cross-sectional curve of Example 4, and FIG. 4 is a drawing showing the area where the cross-sectional curve was measured in Example 4. FIG. 5 is a measurement result of volume area 1 of Example 4, and FIG. 6 is a measurement result of volume area 2 of Example 4. In addition, FIG. 7 is a measured cross-sectional curve of Example 7, and FIG. 8 is a drawing showing the area where the cross-sectional curve was measured in Example 7. FIG. 9 is a measurement result of volume area 1 of Example 7, and FIG. 10 is a measurement result of volume area 2 of Example 7. In addition, FIG. 11 is a measured cross-sectional curve of Comparative Example 7, and FIG. 12 is a drawing showing the area where the cross-sectional curve was measured in Comparative Example 7. FIG. 13 shows the measurement results of volume area 1 of Comparative Example 7, and FIG. 14 shows the measurement results of volume area 2 of Comparative Example 7. The contact area ratios are 54% for Example 4, 41% for Example 7, and 10% for Comparative Example 7. In addition, in FIG. 6 (Example 4), FIG. 10 (Example 7), and FIG. 14 (Comparative Example 7), the darker colored area represents the surface up to a depth of 30 μm from the surface. Since FIG. 14 has fewer darker colored areas compared to FIG. 6 and FIG. 10, it can be seen that the area ratio of the portion up to a depth of 30 μm from the surface is low in Comparative Example 7.

[0099] The ratio of the Sm, Rz, and the area (contact area) of the portion from the surface to a depth of 30 μm of the surface protective layer can be appropriately set by 1) containing fine particles described later, or 2) performing embossing using an embossed plate having irregularities representing the desired Sm, Rz, and the area (contact area) of the portion from the surface to a depth of 30 μm.

[0100] The embossing method is not particularly limited; for example, a preferred method may be to heat and soften the outer surface of the surface protection layer, press and shape it using an embossing plate, and then cool it. Depending on the material of the final product, such as a cosmetic sheet or the surface protection layer, for example, the outer surface of a transparent resin layer may be heat and softened, press and shape it using an embossing plate, and then form a surface protection layer thereon.

[0101] For embossing, known single-wafer or rotary embossing machines are used.

[0102] It is preferable that the surface protection layer be transparent when a patterned layer is formed on the lower layer.

[0103] The resin constituting the surface protection layer is preferably a curable resin, such as a thermosetting resin or an ionizing radiation-curing resin (e.g., an electron beam-curing resin). In particular, from the perspective of resistance to corrosion due to high surface hardness, retention of convex shape, and productivity, it is preferable for the surface protection layer to include an ionizing radiation-curing resin, and it is even more preferable for the resin constituting the surface protection layer to be an ionizing radiation-curing resin.

[0104] Examples of thermosetting resins 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 cocondensation resin, silicon resin, polysiloxane resin, etc.

[0105] Curing agents such as crosslinking agents and polymerization initiators, and polymerization promoters may be added to the above resin. For example, as curing agents, isocyanates, organic sulfonates, etc., may be added to unsaturated polyester resins or polyurethane resins, organic amines, etc., may be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide, radical initiators such as azoisobutylnitrile, etc., may be added to unsaturated polyester resins.

[0106] A method for forming a surface protective layer with a thermosetting resin can be, for example, a method of applying a solution of a thermosetting resin using a coating method such as a roll coat method or a gravure coat method, and then drying and curing it.

[0107] Ionizing radiation-curable resins are not limited to any type of resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. For example, one or more types of prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups within the molecule that can be cross-linked by irradiation with ionizing radiation may be used. Examples include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

[0108] Ionizing radiation includes visible light, ultraviolet rays (near-ultraviolet, vacuum ultraviolet, etc.), X-rays, electron beams, ion rays, etc., but among these, ultraviolet rays and / or electron beams are preferred.

[0109] Light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps can be used as ultraviolet sources. The wavelength of ultraviolet light is approximately 190 to 380 nm.

[0110] As an electron source, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaft type, resonant transformer type, isolation core transformer type, linear type, dynamiteron type, and high frequency type may be used. The energy of the electron beam is preferably about 100 to 1000 keV, and more preferably about 100 to 300 keV. The irradiation dose of the electron beam is preferably about 2 to 15 Mrad.

[0111] Ionizing radiation-curing resins are sufficiently cured when irradiated with electron beams, but when cured by irradiating with ultraviolet rays, it is desirable to add a photopolymerization initiator (sensitizer).

[0112] In the case of a resin system having radical polymerizable unsaturated groups, at least one photopolymerization initiator may be used, such as acetophenones, benzophenones, thioxantones, benzoin, benzoin methyl ether, mihiller benzoyl benzoate, mihiller ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N,N-dimethylaminobenzoate. In addition, in the case of a resin system having cationic polymerizable functional groups, at least one may be used, such as aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and furyloxysulfoxonium diallyl iodocilate salts.

[0113] The amount of photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0114] The thickness of the surface protective layer may be within a range that does not impair the effects of the present invention and is not particularly limited, but is preferably 1 to 200 μm, more preferably 1 to 100 μm, even more preferably 5 to 50 μm, and particularly preferably 10 to 40 μm.

[0115] The surface protective layer may contain fine particles. Examples of fine particles include inorganic fillers such as silica, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, abrasive, glass fiber, etc.; and organic material powders or beads such as acrylic, cross-linked alkyl, cross-linked styrene, benzoguanamine resin, urea-formaldehyde resin, phenolic resin, polyethylene, nylon, etc. One or more types of the fine particles may be used.

[0116] The average particle diameter of the fine particles is preferably greater than or equal to the thickness of the surface protection layer, and to exhibit resistance, it is preferably less than “thickness of the surface protection layer + 40 μm” and more preferably less than “thickness of the surface protection layer + 30 μm”.

[0117] The average particle diameter of the fine particles can be measured by known methods such as laser diffraction, the Coulter counter method, and the sedimentation method. Furthermore, the above average particle diameter refers to the mode diameter.

[0118] The fine particle content in the surface protection layer is preferably 3 to 50 parts by mass per 100 parts by mass of the resin component forming the surface protection layer, and more preferably 5 to 30 parts by mass.

[0119] Silicone may be added to the surface protection layer. When silicone is added to the surface protection layer, the amount of silicone added is preferably 0.1 to 1 part by mass per 100 parts by mass of the resin (resin component) constituting the surface protection layer, and more preferably 0.1 to 0.5 parts by mass, from the perspective of achieving both ease of wiping and difficulty of slipping.

[0120] In the surface protective layer, various additives such as solvents, coloring agents such as dyes and pigments, fillers such as inorganic fillers, defoaming agents, leveling agents, thixotropic agents, flame retardants, antibacterial agents, antiviral agents, and anti-allergens may be added as needed.

[0121] As for the inorganic filler, it can be used as a means to impart a predetermined surface appearance to the surface protection layer by including an inorganic filler larger than the layer thickness of the surface protection layer in the surface protection layer. In addition, the inorganic filler can be used as a matte agent, and by including the inorganic filler in the surface protection layer, an effect of suppressing the curing shrinkage of the surface protection layer can also be expected. Therefore, in the present invention, it is preferable that the inorganic filler be surface-treated (hydrophobized). Furthermore, among these additives, it is preferable to include at least one selected from the group consisting of antibacterial agents, antiviral agents, and anti-allergen agents in the outermost surface protection layer to facilitate obtaining the effect.

[0122] Examples of inorganic fillers include silica, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, adamantium, glass fiber, etc.

[0123] The method of surface treating (hydrophobizing) inorganic fillers is not particularly limited and can be performed using known methods. Examples include a method of hydrophobizing inorganic fillers with a silicone oil-based treatment agent; a method of hydrophobizing inorganic fillers with the silicone oil-based treatment agent described above after treating inorganic fillers with an alkylsilazane-based treatment agent, a trimethylsilylating agent and / or an alkoxysilane; a method of treating inorganic fillers with a silicone oil-based treatment agent and then treating them with a trimethylsilylating agent or an alkylsilazane-based treatment agent; a method of hydrophobizing inorganic fillers with an alkoxysilane; a method of treating inorganic fillers with a silicone oil-based treatment agent, or a silicone oil-based treatment agent and an alkoxysilane after treating them with an alkoxysilane; and a method of treating inorganic fillers using a dimer diol siloxane and / or trimethylsilanol or cyclic siloxane. In addition, in addition to the hydrophobic treatment method described above, various coupling agents such as silane coupling agents, titanate-based coupling agents, and aluminate-based coupling agents; surfactants such as phosphate-based and fatty acid-based agents; and methods of treatment using oils, stearic acid, etc., can also be cited as hydrophobic treatment methods. Hereinafter, all of the products described above for hydrophobizing untreated inorganic fillers (e.g., treatment agents such as silicone oil-based treatment agents, silane coupling agents, surfactants, etc.) are collectively referred to as hydrophobic treatment agents.

[0124] The method of hydrophobizing an inorganic filler with a hydrophobizing agent is not particularly limited and can be performed by known methods. Examples include a method of adding (e.g., spraying) a stock solution of the hydrophobizing agent or a solution of the hydrophobizing agent diluted in water or an organic solvent to an untreated inorganic filler; a method of treating (e.g., immersing) an untreated inorganic filler in a stock solution of the hydrophobizing agent, an aqueous solution containing the hydrophobizing agent, or an organic solvent containing the hydrophobizing agent, and then drying it (wet treatment method). Through such treatment, a part or all of the surface of the inorganic filler may be (a) coated with the hydrophobizing agent, (b) adsorbed with the hydrophobizing agent, or (c) coated with and adsorbed with the hydrophobizing agent (a combination of (a) and (b)). As a result, a hydrophobized inorganic filler can be obtained. In addition, a single type of hydrophobizing agent may be used alone or a combination of two or more types.

[0125] The above antimicrobial agents include inorganic and organic antimicrobial agents. In particular, inorganic antimicrobial agents are preferred because they generally have higher safety and excellent durability and heat resistance compared to organic antimicrobial agents. An inorganic antimicrobial agent is a metal with antimicrobial properties, such as silver, copper, and zinc, supported on various inorganic carriers. When contained in a surface protective layer, the amount of antimicrobial agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be appropriately adjusted depending on the type of antimicrobial agent.

[0126] The above antiviral agents can generally be broadly classified into organic and inorganic types. Organic antiviral agents include quaternary ammonium salts, quaternary phosphonium salts, pyridine, pyrithione, benzimidazole, organic iodine, isothiazoline, anionic, and ether types. Inorganic antiviral agents include those in which metal ions such as silver, copper, and zinc are supported on a carrier such as zeolite, apatite, zirconia, glass, or molybdenum oxide. When contained in a surface protective layer, the amount of antiviral agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be appropriately adjusted depending on the type of antiviral agent.

[0127] Among the above organic antiviral agents, benzimidazole-based antiviral agents, anionic-based antiviral agents, or ether-based antiviral agents that maintain a particle shape are particularly suitable for use. Here, maintaining a particle shape means existing in a particle state without dissolving within the composition (ink before curing) that becomes the curable resin of the surface protective layer. Because of this, during the process of forming the surface protective layer, particles of the imidazole-based compound, particles of the anionic-based compound, or particles of the ether-based compound are easily brought to the surface, and it is easy to make the particles of the imidazole-based compound, anionic-based compound, or ether-based compound localized on the outermost surface side of the surface protective layer. Furthermore, by localizing the particles of the imidazole-based compound, particles of the anionic-based compound, or particles of the ether-based compound on the outermost surface side of the surface protective layer, the amount of antiviral agent required to obtain a predetermined antiviral property can be reduced, and thus it is easy to suppress the deterioration of the scratch resistance of the surface protective layer.

[0128] As for the above-mentioned anionic antiviral agent, it is preferable to include, for example, a styrene resin, a styrene polymer derivative compound, and an unsaturated carboxylic acid derivative compound. Furthermore, it is preferable that the above-mentioned styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound include at least one structure among the structures of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and it is even more preferable to include all of them. This is because viruses exist in two main types based on the presence or absence of an envelope, and it is believed that the structures of antiviral agents capable of effectively inhibiting the activity of each are different. Therefore, for example, if an effect is expected only against the influenza virus, which is a non-envelope virus, it is sufficient to include only a styrene polymer derivative compound, and among them, there are cases where sufficient effect is obtained even if only a styrene resin monomer is included.

[0129] As for the above-mentioned inorganic antiviral agents, silver-based antiviral agents are preferred from the perspective that they have no biological toxicity and excellent safety, and among them, phosphate-based free silver supported compounds or silver zeolite compounds and molybdenum oxide silver double salt compounds are even more preferred because they exhibit antiviral performance even in small amounts, so the amount added can be suppressed.

[0130] When the above-mentioned silver-based antiviral agent is contained in the surface protective layer, discoloration may occur depending on the surface protective layer (discoloration may occur due to heat and light in the paint state after addition, or discoloration may occur due to heat and light after the surface protective layer is formed), but this can be improved by adding UV blockers, light stabilizers, etc. in a timely manner. For example, regarding the above-mentioned molybdenum oxide silver double salt compound, a discoloration improvement effect can be expected by using a benzotriazole-based compound.

[0131] The above anti-allergen agent comprises either an inorganic compound or an organic compound, and may be used as a single unit or a mixture of two or more other types. As for the inorganic compound, it is preferable that it be a material formed by supporting a metal. When contained in a surface protective layer, the amount of anti-allergen agent added is preferably 0.1 to 10 parts by mass per 100 parts by mass of the resin component of the surface protective layer, but the details can be appropriately adjusted depending on the type of anti-allergen agent.

[0132] A method for forming a surface protection layer including an ionizing radiation curable resin may be, for example, a method of forming a surface protection layer by curing the ionizing radiation curable resin after applying a solution (resin composition for forming a surface protection layer) containing (1) a resin such as an ionizing radiation curable resin and (2) other resins, fine particles, ultraviolet absorbers, antibacterial agents, and various additives as needed by a coating method such as a gravure coating method or a roll coating method.

[0133] (Back primer layer)

[0134] On the back side of the substrate sheet (the side opposite to the side where the pattern layer is laminated), a back primer layer may be formed as needed. For example, this is effective when producing a decorative board by laminating a decorative sheet and a substrate (adhesive).

[0135] The primer layer on the back can be formed by applying a known primer agent to a substrate sheet. Examples of primer agents include urethane resin-based primer agents containing, for instance, acrylic modified urethane resin (acrylurethane-based resin), primer agents containing urethane-cellulose-based resin (e.g., a resin formed by adding hexamethylene diisocyanate to a mixture of urethane and nitride), and resin-based primer agents containing a block copolymer of acrylic and urethane. Additives may be incorporated into the primer agent as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, light stabilizers, etc. The amount of additives incorporated can be appropriately set according to the product characteristics.

[0136] The amount of primer applied is not particularly limited, but is typically 0.1 to 100 g / m², preferably 0.1 to 50 g / m².

[0137] The thickness of the primer layer is not particularly limited, but is typically 0.01 to 10 μm, preferably 0.1 to 1 μm.

[0138] (Backer layer)

[0139] On the back side of the substrate sheet, a backer layer (a synthetic resin layer for increasing resistance or mitigating the influence of the substrate (adhesive)) may be formed. Furthermore, the above resistance refers to indentation, particularly when a load is applied partially. Although the cosmetic sheet of the present invention has sufficient resistance even without a backer layer, forming a backer layer can further enhance overall performance such as resistance.

[0140] As a method for forming a backer layer, extrusion molding of molten resin is suitable, for example, extrusion molding using a T-die is suitable.

[0141] Methods for bonding the back side of a substrate sheet and a backer layer include bonding the backer layer obtained by extruding the substrate sheet and molten resin by heat fusion, and bonding by forming an adhesive layer (and, if necessary, a primer layer) between the substrate sheet and the backer layer.

[0142] Examples of resins constituting the backer layer include, but are not limited to, thermoplastic resins such as polyethylene, polypropylene (PP), polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, amorphous polyethylene terephthalate (A-PET), highly heat-resistant polyalkylene terephthalate [e.g., polyethylene terephthalate in which a portion of ethylene glycol is substituted with 1,4-cyclohexanedimethanol or diethylene glycol, etc., so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate (PBT), polycarbonate, polyarylate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, ABS (acrylonitrile-butadiene-styrene copolymer), etc. These resins can be used alone or in combination of two or more types.

[0143] The thickness of the backer layer can be appropriately set according to the purpose and method of use of the final product, and is generally preferred to be 100 to 800 μm. Among these, 100 to 600 μm is more preferred.

[0144] If necessary, known easy-adhesion treatments, such as corona discharge treatment, plasma treatment, degreasing treatment, or surface roughening treatment, may be applied to the adhesive surface of the backer layer. Additionally, a primer layer may be further formed on the back surface to improve adhesion with the substrate.

[0145] (Vesicleization of various additives included in each layer of the cosmetic sheet)

[0146] It is preferable that the various additives (such as inorganic fillers added to the primer layer or surface protection layer) added to each of the aforementioned layers of the cosmetic sheet of the present invention be vesicleized. The method for vesicleizing the various additives is not particularly limited and can be vesicleized by known methods, among which the supercritical reverse phase evaporation method is preferred.

[0147] In addition to the supercritical reverse-phase evaporation method, vesicle formation methods include the Bangham method, extrusion method, hydration method, reverse-phase evaporation method, and freeze-thaw method. To briefly explain these vesicle formation methods, the Bangham method involves placing chloroform or a chloroform / methanol mixed solvent into a container such as a flask, and then adding and dissolving phospholipids. Subsequently, the solvent is removed using an evaporator to form a thin film containing lipids; after adding a dispersion of additives, vesicles are obtained by hydrating and dispersing the solution using a vortex mixer. The extrusion method involves preparing a phospholipid solution from a thin film and obtaining vesicles by passing it through a filter instead of the mixer used for external perturbation in the Bangham method. The hydration method is almost identical to the Bangham method in preparation, but vesicles are obtained by dispersing the solution through gentle stirring without using a mixer. The reverse phase evaporation method is a method of obtaining a vesicle by dissolving a phospholipid in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water. The freeze-thaw method is a method of obtaining a vesicle by using cooling and heating as external perturbations and repeating this cooling and heating.

[0148] The supercritical reverse-phase evaporation method is described in detail below. The supercritical reverse-phase evaporation method is a method of forming a capsule-type vesicle containing various additives as encapsulating materials by adding an aqueous phase containing various additives as encapsulating materials, which are water-soluble or hydrophilic, to a mixture in which a substance forming the outer membrane of a vesicle is uniformly dissolved in carbon dioxide under supercritical conditions or at a temperature or pressure above the supercritical point. Furthermore, carbon dioxide in a supercritical state refers to carbon dioxide in a supercritical state at a critical temperature (30.98°C) and a critical pressure (7.3773 ± 0.0030 MPa), and carbon dioxide under a temperature or pressure above the critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical condition. By the above method, a single-layer lamellar vesicle with a diameter of 50 to 800 nm can be obtained. Generally, a vesicle is a general term for a vesicle containing a liquid phase inside, having a closed, spherical membrane structure; in particular, those whose outer membrane is composed of biological lipids such as phospholipids are called liposomes.

[0149] Examples of the above phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, glycerophospholipids such as egg lecithin, hydrogenated egg lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramidephosphorylethanolamine, and ceramidephosphorylglycerol.

[0150] In addition, nonionic surfactants or dispersants such as mixtures of these with cholesterol or triacylglycerol can be used as materials constituting the outer membrane.

[0151] As the above nonionic surfactant, one or more types such as polyglycerin ether, dialkylglycerin, polyoxyethylene hardened castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, and polyoxyethylene-polycaprolactam copolymer may be used.

[0152] As the above cholesterol types, one or more types such as cholesterol, α-cholestanol, β-cholestanol, cholestan, desmostol (5,24-cholestadien-3β-ol), sodium cholate, and cholecalciferol may be used.

[0153] The outer membrane of the above liposome may be formed from a mixture of phospholipid and a dispersant. In the cosmetic sheet of the present invention, by making the outer membrane of the liposome a phospholipid, the compatibility between the resin composition, which is the main component of each layer, and various additives can be made good.

[0154] (Method for manufacturing cosmetic sheets)

[0155] The cosmetic sheet of the present invention can be obtained by forming at least the aforementioned surface protection layer on the outermost surface. For example, it is obtained by laminating a patterned layer, a transparent adhesive layer, a transparent resin layer, and a primer layer on a substrate sheet, and then forming a surface protection layer on the outermost surface.

[0156] In addition, when performing embossing on a cosmetic sheet, it may be done after forming a surface protective layer or before forming a surface protective layer. For example, as a specific embodiment, 1) a pattern layer, a transparent resin layer, and a primer layer may be formed sequentially on a substrate sheet, then a surface protective layer may be formed, and finally, embossing may be performed. Also, as another specific embodiment, 2) a pattern layer, a transparent resin layer, and a primer layer may be formed sequentially on a substrate sheet, then embossing may be performed, and finally, a surface protective layer may be formed. Also, as yet another specific embodiment, 3) a pattern layer and a transparent resin layer may be formed sequentially on a substrate sheet, then embossing may be performed, then a primer layer may be formed, and finally, a surface protective layer may be formed. When adjusting the Sm, Rz, and area ratio of the portion from the surface to a depth of 30 μm of the surface protective layer through embossing, it is preferable to perform embossing after forming the surface protective layer.

[0157] For example, embossing can be performed by transferring an embossing pattern to the pattern printing side of the decorative sheet at a sheet temperature of 120°C to 160°C and a pressure of 10 to 40 kg / ㎠.

[0158] 2. Decorative board

[0159] The decorative plate of the present invention is a decorative plate having the above-mentioned decorative sheet on a substrate. The decorative sheet may be laminated on the substrate such that the surface protective layer of the decorative sheet becomes the outermost surface layer.

[0160] The substrate (adhesive) is not limited and may be a known decorative board. Examples include wood materials, metals, ceramics, plastics, glass, etc. In particular, the decorative sheet of the present invention is suitable for use with wood materials. Specifically, wood materials include sliced ​​veneers, wood veneers, wood plywood, wood fiberboard, particle board, medium-density fiberboard (MDF), etc., made from various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melapy.

[0161] The lamination method is not limited, and, for example, a method of attaching a decorative sheet to a substrate using an adhesive may be adopted. The adhesive may be appropriately selected from known adhesives depending on the type of substrate, etc. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc. These adhesives may be used alone or in combination of two or more types.

[0162] The decorative panel manufactured in this manner can be used, for example, as an interior material for buildings such as walls, ceilings, and floors; as a decorative panel for the surface of windows and doors such as window frames, doors, and railings; as a decorative panel for the surface of cabinets such as furniture, electronic products, and OA equipment. In particular, the decorative panel of the present invention can be suitably used as a decorative material for floors.

[0163] Examples

[0164] The present invention will be explained more specifically below by presenting examples and comparative examples. However, the present invention is not limited to the examples.

[0165] The following components were prepared as components of the resin composition constituting the surface protective layer.

[0166] · Bi-functional urethane acrylate oligomer A (polyol component is polyesterdiol, Tg: 25℃, molecular weight 1200)

[0167] · Bi-functional urethane acrylate oligomer B (polyol component is polyetherdiol, Tg: -55℃, molecular weight 5000)

[0168] · Bi-functional urethane acrylate oligomer C (polyol component is polyesterdiol, Tg: 25℃, molecular weight 1500)

[0169] · Bi-functional urethane acrylate oligomer D (polyol component modified into dicyclohexylmethane diisocyanate (hydrogenated MDI) of polyetherdiol, Tg: -20℃, molecular weight 5000)

[0170] · Tri-functional urethane acrylate oligomer (aliphatic urethane acrylate having an isocyanurate backbone formed by a trimer of hexamethylene diisocyanate as the polyol component, Tg: 100°C or higher, molecular weight 1500)

[0171] · 6-function aliphatic urethane acrylate oligomer (Tg: 200°C or higher, molecular weight 1500, UA306H manufactured by Kyoei Co., Ltd.)

[0172] · Filler: (Average particle diameter 10 µm silica)

[0173] · Filler: (Average particle diameter 14 µm silica)

[0174] · Filler: (Average particle diameter 20 µm silica)

[0175] In addition, as embossing plates used for embossing processing, sand grain, bark grain, wood grain, matte grain, leather grain, and stone grain embossing plates were prepared. Furthermore, even within the same type of embossing plate, plates with different Rz and Sm values ​​were also prepared.

[0176] Example 1

[0177] (Production of cosmetic sheets)

[0178] After performing corona discharge treatment on the surface and back side of a substrate sheet containing a colored polypropylene film with a thickness of 60 μm, a wood grain pattern layer with a thickness of 4 μm was formed on the substrate sheet by gravure printing using a colored ink in which an acrylic resin was used as a binder resin. In addition, on the side opposite to the pattern layer of the substrate sheet, a back primer layer with a thickness of 2 μm was formed by gravure printing using a resin composed of 100 parts by mass of acrylic urethane resin and 5 parts by mass of hexamethylene diisocyanate. A coating solution containing a two-component curable urethane resin was applied onto the pattern layer to form a transparent adhesive layer with a thickness of 2 μm. Furthermore, a sheet of polypropylene resin was laminated onto the adhesive layer using an extrusion lamination method to form a transparent resin layer with a thickness of 80 μm. After performing corona discharge treatment on the surface of the transparent resin layer, a primer layer with a thickness of 1 μm was formed by coating the transparent resin layer with a two-component curable urethane resin. Next, a film (13 μm) of a resin composition constituting a surface protection layer as shown below was formed on the primer by a roll-coat method, and then a surface protection layer was formed by irradiating an electron beam under conditions of 175 keV and 5 Mrad (50 kGy) in an environment with an oxygen concentration of 200 ppm or less. In addition, the surface protection layer side was heated with an infrared non-contact heater to soften the substrate sheet and the transparent resin layer, and then a sand grain-like uneven shape was formed by performing embossing by heat and pressure. Thus, a floor decoration sheet was produced. The Martens hardness of the surface protection layer measured on the produced floor decoration sheet was 35 N / mm².

[0179] [Resin composition constituting the surface protective layer]

[0180] ·2-function urethane acrylate oligomer C 100 parts by mass

[0181] · 18 parts by mass of fine particles (spherical silica with a modal diameter of 20 µm).

[0182] (Production of the cosmetic)

[0183] A water-based emulsion adhesive (BA-10L (main component): BA-11B (hardener) = 100:2.5 (mass ratio) manufactured by Japan Coating Resin Co., Ltd.) was uniformly coated onto a medium-density wood fiber board (MDF) with a thickness of 2.5 mm at a rate of 80 g / m², and the adhesive was bonded to the back primer layer side of the floor decorative sheet obtained above and cured at room temperature for 3 days to produce a floor decorative board.

[0184] Examples 2–7, Comparative Examples 1–7

[0185] Cosmetic sheets and cosmetic plates shown in Tables 1 and 2 were produced in the same manner as in Example 1, except for appropriately changing the components and content of the resin composition constituting the surface protective layer, the martens hardness, and the type of embossed shape.

[0186] The following measurements were performed on the cosmetic sheets or cosmetic plates produced in the examples and comparative examples.

[0187] [Martens Hardness Measurement]

[0188] The Martens hardness of the cross-sectional direction of the surface protection layer was measured by the method described above. The results are shown in Tables 1 and 2. In addition, the Martens hardness values ​​in the tables represent the average of 10 measurements.

[0189] [Measurement of Rz and Sm]

[0190] Sm was measured by a measurement method based on JIS B0601 (1994), and Rz was measured by a measurement method based on JIS B0601 (2001). The above Rz and Sm were obtained by measuring the surface roughness of the decorative panel. The surface roughness was measured using a surface roughness shape measuring instrument (Safcom 120A, manufactured by Tokyo Seimitsu Co., Ltd.). In addition, Rz and Sm in the table represent the average of the measurements taken by measuring the decorative panel three times at different locations.

[0191] [Ratio of the area (contact area) of the portion from the surface to a depth of 30 µm]

[0192] The ratio of the area (contact area) of the portion from the surface of each cosmetic sheet to a depth of 30 μm was measured using a laser microscope VK-X1000 (manufactured by Giensuga Bushiki Kaisha). Specifically, under the condition of a lens magnification of 50x, the total volume area 1 from the surface of the cosmetic sheet was measured for an area of ​​1 cm². Subsequently, the volume area 2 from the surface to a depth of 30 μm was measured, and the ratio of the contact area was calculated based on the following formula.

[0193] (Ratio of contact area (%)) = (Volume area 2 / Volume area 1) × 100

[0194] FIGS. 3 to 14 illustrate examples of measuring the area ratio of the portion of the surface protection layer from the surface to a depth of 30 μm in Example 4, Example 7, and Comparative Example 7, which will be described later. Specifically, FIG. 3 is a measured cross-sectional curve of Example 4, and FIG. 4 is a drawing showing the area where the cross-sectional curve was measured in Example 4. FIG. 5 is a measurement result of volume area 1 of Example 4, and FIG. 6 is a measurement result of volume area 2 of Example 4. In addition, FIG. 7 is a measured cross-sectional curve of Example 7, and FIG. 8 is a drawing showing the area where the cross-sectional curve was measured in Example 7. FIG. 9 is a measurement result of volume area 1 of Example 7, and FIG. 10 is a measurement result of volume area 2 of Example 7. In addition, FIG. 11 is a measured cross-sectional curve of Comparative Example 7, and FIG. 12 is a drawing showing the area where the cross-sectional curve was measured in Comparative Example 7. FIG. 13 shows the measurement results of volume area 1 of Comparative Example 7, and FIG. 14 shows the measurement results of volume area 2 of Comparative Example 7. The ratio of the contact area is 54% for Example 4, 41% for Example 7, and 10% for Comparative Example 7. In addition, in FIG. 6 (Example 4), FIG. 10 (Example 7), and FIG. 14 (Comparative Example 7), the darker colored area represents the surface up to a depth of 30 μm from the surface. Since FIG. 14 has fewer darker colored areas compared to FIG. 6 and FIG. 10, it can be seen that the area ratio of the portion up to a depth of 30 μm from the surface is low in Comparative Example 7.

[0195] The following evaluation was performed on the cosmetic sheets or cosmetic plates produced in the examples and comparative examples.

[0196] (Impact resistance (DuPont impact test))

[0197] Tests were conducted in accordance with JIS K5600-5-3:1999 (General Test Methods for Paints, Part 5: Mechanical Properties of Films, Section 3: Drop Resistance). Specifically, a 500 g spindle was dropped from a height of 30 cm onto the surface of each floor decorative panel of the examples and comparative examples, and the indentation was measured to evaluate the results. The sample size was set to 9 points, and the number of points where cracks occurred out of the 9 points was evaluated. The evaluation criteria are as follows. Here, if the result is + / - or greater, it is evaluated that there are no problems in actual use.

[0198] ++: There are no cracks

[0199] +: 1~2 cracks

[0200] + / -: Uniform 3~8

[0201] -: Everything is cracked

[0202] (Stain resistance)

[0203] 10% of pigment-grade carbon black (CAS1333-86-4) was added to white petroleum jelly (CAS8009-03-8), and applied at a rate of approximately 10 g / m² to the entire surface of each floor-cladding sheet prepared in the examples and comparative examples. Subsequently, the surface was dry-wiped with a cloth (towel fabric) to remove any stains caused by the petroleum jelly, and the surface of each floor-cladding sheet was evaluated by visually inspecting it after wiping. The evaluation criteria are as follows. Here, if the result is + / - or greater, it is evaluated as having no issues in actual use.

[0204] ++: There are no stains

[0205] +: The stain is not noticeable

[0206] + / -: There is a faint stain

[0207] -: There are stain marks

[0208] (Anti-slip properties (OY·PSM))

[0209] For each decorative panel, the slip resistance value (CSR value) by socks was measured using the sliding tester (OY·PSM) of Tokyo High School Daigaku. The evaluation criteria are as follows. In addition, a smaller value indicates that it is easier to slip, and the range of slip resistance values ​​that humans find comfortable is within the range of 0.30 to 0.50.

[0210] +: Measurement value 0.35 or higher and 0.50 or lower (difficult to slip)

[0211] + / -: Measurement is 0.30 or higher and less than 0.35 (slightly difficult to slide)

[0212] -: Measurement value 0.25 or higher and less than 0.30 (slippery)

[0213] (Anti-slip durability)

[0214] As a treatment to accelerate the loss of uneven surface shape, steel wool (Nippon Steel Wool Co., Ltd., Material: Iron, Part No.: #1, Quality: Medium) was used, and a sliding treatment was performed under a load of 300 g / ㎡ until the gloss of the sheet surface changed slightly. Subsequently, an evaluation was conducted in the same manner as the above anti-slip performance evaluation.

[0215] (Chairmanship)

[0216] The cosmetic sheet was observed visually from the surface protection layer side, and its aesthetic appeal was evaluated according to the following criteria. Here, a result of + / - or greater is considered to be acceptable for actual use.

[0217] ++: The surface irregularities created by the embossing match the design of the pattern underneath, and it is a design that feels more textured than the real thing.

[0218] +: The surface irregularities created by the embossing match the design of the pattern underneath, making it feel authentic.

[0219] + / -: The surface irregularities caused by embossing match the design of the pattern underneath, but the irregularities are small, making it difficult to perceive the design as authentic.

[0220] -: The surface irregularities caused by the embossing differ from the design of the pattern underneath, and the design feels jarring.

[0221] The results are shown in Table 1 and Table 2.

[0222]

[0223]

[0224] Example 8

[0225] A cosmetic sheet was prepared in the same manner as in Example 1, except that 3 parts by mass of a phosphate-based glass silver-supported compound (manufactured by Koagaras / PG-711) was added as an antiviral agent to 100 parts by mass of the resin composition constituting the surface protective layer used in Example 1.

[0226] The following characteristics were evaluated for the cosmetic sheet produced in Example 8.

[0227] (Antiviral performance)

[0228] With respect to the cosmetic sheet prepared in Example 8, an antiviral performance test was performed in accordance with the antiviral test method (ISO 21702), and the antiviral activity against the influenza virus was evaluated based on the following evaluation criteria. The evaluation criteria are as follows.

[0229] +: Antiviral activity was 2.0 or higher

[0230] -: Antiviral activity was less than 2.0

[0231] The results are shown in Table 3.

[0232]

[0233] Example 9

[0234] A cosmetic sheet was prepared in the same manner as in Example 1, except that an anionic phenolic material having anti-allergenic properties (manufactured by DIC, “EXP20530A”) and a zinc-based material having anti-allergenic properties (manufactured by DIC, “EXP20530B”) were added as anti-allergen agents to the resin composition constituting the surface protection layer used in Example 1. The amount of the anionic phenolic material and the zinc-based material added was such that, with the resin composition constituting the surface protection layer including the anionic phenolic material and the zinc-based material being 100 mass%, the amount added was 23 mass% each in terms of solid content ratio.

[0235] The following characteristics were evaluated for the cosmetic sheet produced in Example 9.

[0236] (Anti-allergen performance)

[0237] The anti-allergen performance of the cosmetic sheet prepared in Example 9 was evaluated. Specifically, the cosmetic sheet prepared in Example 9 was cut into small pieces, and the amount of allergen after immersion in an aqueous solution of mite allergens for one day was visually confirmed using a horizontal elongation chromatography method (Mighty Checker) and evaluated according to the following evaluation criteria. The evaluation criteria are as follows.

[0238] +: A decrease in allergen levels was confirmed (dust mite allergen level was rated as + or lower (i.e., approximately 100 mites / m² or less)

[0239] -: Could not confirm a decrease in allergen amount (dust mite allergen level judgment exceeded + judgment)

[0240] The results are shown in Table 4.

[0241]

[0242] It was confirmed from the difference in color intensity of the checker that the cosmetic sheet of Example 9 has anti-allergen performance.

[0243] Example 10

[0244] A backer layer having a thickness of 120 μm was formed by laminating a polypropylene resin layer on the back side of the cosmetic sheet produced in Example 1 using a melt extrusion lamination method. In addition, a corona discharge treatment was performed on the back side of the backer layer, and a back primer layer (thickness 2 μm) was formed to produce a cosmetic sheet, and a cosmetic plate was produced in the same manner as in Example 1.

[0245] The following characteristics were evaluated for the decorative panels produced in Examples 1 and 10.

[0246] (Impact resistance (DuPont impact test))

[0247] Tests were conducted in accordance with JIS K5600-5-3:1999 (General Test Methods for Paints, Part 5: Mechanical Properties of Films, Section 3: Drop Resistance). Specifically, a 500 g spindle was dropped from a height of 30 cm onto the surface of the decorative panels of Examples 1 and 10 for evaluation. The sample size was set to 9 points, and the evaluation was conducted by visually confirming the number of cracks and indentations among the 9 points. The evaluation criteria are as follows. Here, a value of + or higher is evaluated as having no issues in actual use.

[0248] ++++: There are no cracks

[0249] +++: There are 1 to 2 cracks and no noticeable depressions.

[0250] ++: 1~2 cracks

[0251] +: 3~8 cracks

[0252] -: Everything is cracked

[0253] The results are shown in Table 5.

[0254]

[0255] Compared to the cosmetic sheet of Example 1, the cosmetic sheet of Example 10 does not show noticeable indentation, so it was confirmed that the cosmetic sheet of Example 10 has improved impact resistance. Explanation of the symbols

[0256] 1: Floor vanity sheet 2: Back primer layer 3: Entry Sheet 4: Pattern-shaped layer 5: Adhesive layer 6: Transparent resin layer 7: Primer layer 8: Surface protection layer 9: Emboss pattern (wood grain conduit groove)

Claims

Claim 1 A cosmetic sheet having a surface protection layer on the outermost surface, wherein (1) the Martens hardness of the surface protection layer is 30 to 170 N / mm², and the Martens hardness is a value obtained by measuring the Martens hardness of the cross-section by pressing a diamond indenter into a position avoiding the fine particles when the surface protection layer contains fine particles, (2) the surface protection layer has irregularities, and the irregularities have an embossed shape of sand grain, wood grain, bark grain, stone grain, or leather grain, and the average spacing (Sm) of the irregularities is 180 μm to 950 μm, (3) the maximum height (Rz) of the surface protection layer is 10 to 45 μm, and (4) the area ratio of the portion from the surface to a depth of 30 μm is 40% or more. Claim 2 In claim 1, a cosmetic sheet having a martensitic hardness of 70 to 150 N / mm². Claim 3 A cosmetic sheet according to claim 1 or 2, wherein Rz is 10 to 19 μm. Claim 4 A cosmetic sheet according to claim 1 or 2, wherein Sm is 450 to 750 μm. Claim 5 A cosmetic sheet according to claim 1 or 2, wherein the surface protective layer has an area ratio of 50% to 90% of the portion higher than a depth of 30 μm from the surface. Claim 6 A cosmetic sheet according to claim 1 or 2, wherein the surface protective layer has an area ratio of 60% to 85% of the portion higher than a depth of 30 μm from the surface. Claim 7 A cosmetic sheet according to claim 1 or 2, wherein the surface protective layer contains an ionizing radiation-curing resin. Claim 8 A cosmetic sheet according to claim 1 or 2, wherein the thickness of the surface protective layer is 10 to 40 μm. Claim 9 A cosmetic sheet according to claim 1 or 2, wherein the surface protective layer contains at least one selected from the group consisting of antibacterial agents, antiviral agents, and anti-allergen agents. Claim 10 A cosmetic sheet according to claim 1 or 2, having a pattern-shaped layer, a transparent resin layer, and the surface protection layer in sequence on a substrate sheet. Claim 11 A cosmetic sheet according to claim 1 or 2, wherein a patterned layer, a transparent resin layer, and the surface protection layer are sequentially formed on a substrate sheet, and at least a backer layer is laminated on the back side of the substrate sheet. Claim 12 A decorative plate having the decorative sheet described in paragraph 1 or 2 on the substrate. Claim 13 In Clause 12, the above description is a decorative board that is a wood veneer, wood plywood, wood fiberboard, or particle board.

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