Decorative sheet and decorative material

Abstract

Provided are a decorative sheet and a decorative material having high scratch resistance and antiviral properties. The decorative sheet has a base sheet, an adhesive layer, a surface protective layer containing an antiviral agent, and a thermoplastic resin layer, at least one of the surface protective layer or the thermoplastic resin layer containing a nucleating agent or inorganic particles, the antiviral agent being added in an amount of 0.2 to 10 parts by mass with respect to the surface protective layer.

Description

Technical Field

[0001] This disclosure relates to decorative sheets and decorative materials. Background Technology

[0002] Previously, many decorative sheets using olefin-based resins were proposed as alternatives to decorative sheets made of polyvinyl chloride (PVC). However, their scratch resistance was poor and inferior to that of conventional PVC sheets (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-188941 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] In recent years, the demand for antiviral properties has increased, making the development of antiviral products a top priority. However, a challenge exists: due to wear or damage to the decorative panels, the outermost surface is worn down, reducing antiviral properties. This is particularly true for flooring decorative panels, where they are used as flooring materials for outdoor footwear such as shoes or high heels. Problems include poor scratch resistance, easy damage to the surface of the flooring decorative material, and significant wear down of the outermost surface containing antiviral agents.

[0008] The purpose of this disclosure is to provide decorative sheets and decorative materials that are highly resistant to damage and have antiviral properties.

[0009] Solution for solving the problem

[0010] To address the aforementioned issues, one aspect of the decorative sheet disclosed herein is characterized by comprising a substrate sheet, an adhesive layer, a surface protective layer, and a thermoplastic resin layer, wherein the surface protective layer contains an antiviral agent, and at least one of the surface protective layer or the thermoplastic resin layer contains a nucleating agent or inorganic particles, and the amount of the antiviral agent added relative to the surface protective layer is 0.2 parts by mass to 10 parts by mass.

[0011] The effects of the invention

[0012] According to one aspect of this disclosure, decorative sheets and decorative materials with high damage resistance and antiviral properties can be provided. Attached Figure Description

[0013] [ Figure 1 [A cross-sectional view illustrating an example of the configuration of a decorative sheet according to the first embodiment of the present invention.]

[0014] [ Figure 2[A cross-sectional view illustrating an example of the configuration of a decorative sheet according to the second embodiment of the present invention.]

[0015] [ Figure 3 [A cross-sectional view illustrating an example configuration of the decorative sheet according to the third embodiment of the present invention.]

[0016] [ Figure 4 [A cross-sectional view illustrating a configuration example of the decorative material according to the fourth embodiment of the present invention.] Detailed Implementation

[0017] One embodiment of this disclosure will be described with reference to the accompanying drawings.

[0018] The configuration shown in the accompanying drawings is schematic, and the relationship between thickness and planar dimensions, the ratio of thickness of each layer, etc., differ from the actual situation. Furthermore, the embodiments shown below exemplify configurations used to concretize the technical concept of this disclosure. Regarding the technical concept of this disclosure, the materials, shapes, structures, etc., of the constituent components are not limited to those described below. The technical concept of this disclosure can be modified in various ways within the technical scope defined by the claims.

[0019] <First Embodiment>

[0020] (Composition of decorative pieces)

[0021] use Figure 1 The basic structure of the decorative sheet according to the first embodiment of this disclosure will be described. Figure 1 This is a cross-sectional view illustrating a configuration example of the decorative sheet 10 according to the first embodiment of this disclosure.

[0022] like Figure 1 As shown, in one embodiment of the present invention, a decorative sheet 10 has a colored pattern layer 12, an adhesive layer 13, and a surface protective layer 14 sequentially stacked on one side of a substrate sheet 11. Each layer will be described in detail below.

[0023] (Substrate sheet)

[0024] The substrate sheet 11 is a layer that serves as the substrate of the decorative sheet 10. In this embodiment, a thermoplastic resin can be used as the substrate sheet 11. There are no particular limitations on the thermoplastic resin; for example, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer can be used; olefin copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylate copolymer, and ethylene-unsaturated carboxylic acid copolymer metal neutralizer (ionomer) can be used; and polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, and 1,4-cyclohexanediol copolymer polyethylene terephthalate can be used. Polyester resins such as alcohol esters, polyarylates, and polycarbonates; acrylic resins such as poly(meth)acrylonitrile, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)butyl acrylate, and polyacrylamide; polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon; styrene resins such as polystyrene, AS resin, and ABS resin; vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl alcohol acetal, and polyvinyl alcohol butyral; fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer; or mixtures, copolymers, composites, and laminates of two or more of these resins.

[0025] Here, many thermoplastic resins are listed as suitable thermoplastic resins for use in the substrate sheet 11. However, given the high level of public concern about environmental issues in recent years, non-halogen thermoplastic resins are preferred over chlorine-containing (halogen) thermoplastic resins such as polyvinyl chloride resin. In particular, considering various physical properties, processability, versatility, and economic factors, polyolefin resins or polyester resins (amorphous or biaxially stretched) are the most preferred non-halogen thermoplastic resins.

[0026] As a polyolefin resin, it is appropriate to select from the many types listed above, depending on the intended use of the decorative sheet 10. In particular, polypropylene resins, i.e., homopolymers or copolymers with propylene as the main component, are most suitable for general applications. For example, homopolymers, atactic polypropylene resins, block polypropylene resins, etc., can be used alone or appropriately combined, or resins obtained by further appropriately combining atactic polypropylene can be used. In addition, copolymers containing olefin monomers other than propylene can also be used. For example, propylene-α-olefin copolymers that have a polypropylene crystalline portion and contain 15 mol% or more of α-olefins with 2 to 20 carbon atoms other than propylene, preferably one or two or more comonomers selected from ethylene, butene-1, 4-methylpentene-1, hexene-1, or octene-1, can be used. In addition, modifiers such as low-density polyethylene, ethylene-α-olefin copolymers, ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene copolymer rubbers, styrene-butadiene copolymers, or their hydrogenates, which are commonly used for softening polypropylene resins, can be appropriately added.

[0027] In addition, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers can be added to the substrate sheet 11.

[0028] The thickness of the substrate sheet 11 is preferably in the range of 160 μm to 220 μm, more preferably 180 μm to 190 μm. When the thickness of the substrate sheet 11 is 160 μm or more, it can absorb the unevenness and steps of the floor material used as the base, thereby enabling the installation of the decorative sheet 10 to be completed well. In addition, when the thickness of the substrate sheet 11 is 190 μm or less, a substrate sheet 11 exceeding the required thickness will not be formed, thereby reducing the manufacturing cost of the decorative sheet 10.

[0029] (Colored pattern layer)

[0030] The colored pattern layer 12 is formed on the substrate sheet 11 to attach a pattern for imbuing the design, and is provided as needed. The colored pattern layer 12 may be omitted if the substrate sheet 11 can be colored instead. The colored pattern layer 12 is formed using printing ink or coatings made by dissolving or dispersing a colorant such as a dye or pigment with a suitable binder resin in a suitable diluent. The printing ink or coating is applied using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roller coating. Furthermore, as the binder resin, for example, urethane resins, acrylic resins, vinyl chloride acetate resins, polyimide resins, nitrocellulose, or mixtures thereof can be used, but it is not limited to these. Additionally, any pattern can be used as the pattern, such as wood grain patterns, stone patterns, fabric patterns, abstract patterns, geometric patterns, text, symbols, single-color pigments, or combinations thereof. In addition, to improve the concealment of the decorative piece 10, a concealing layer formed by an opaque printing ink or coating containing many opaque pigments such as titanium dioxide or iron oxide can be provided between the colored pattern layer 12 and the substrate piece 11.

[0031] The thickness of the colored pattern layer 12 is preferably in the range of 3 μm to 20 μm. When the thickness of the colored pattern layer 12 is 3 μm or more, the printing can be clear. When the thickness of the colored pattern layer 12 is 20 μm or less, the printing operability in manufacturing the decorative sheet 10 can be improved, and the manufacturing cost can be reduced.

[0032] In addition, to impart various functions, functional additives such as extender pigments, plasticizers, dispersants, surfactants, adhesive agents, bonding aids, drying agents, curing agents, curing accelerators, and curing delay agents can be added to the colored pattern layer 12.

[0033] Additionally, the colored pattern layer 12 may have, for example, a colored layer that is solidly applied to conceal the color / pattern of the base to which the decorative piece 10 is pasted, and a pattern layer for attaching a design-specific pattern.

[0034] (Adhesive layer)

[0035] The adhesive layer 13 is formed on the colored patterned layer 12 and is provided as needed to bond the substrate sheet 11 to the surface protective layer 14. The adhesive layer 13 may be omitted if the adhesive properties of other layers can be utilized. There are no particular limitations on the type of adhesive used in the adhesive layer 13, but a two-component curing urethane adhesive using an isocyanate-based curing agent is most preferably used. For example, polyester polyols and polyether polyols can be used as the main component of the two-component curing urethane adhesive; and for example, toluene diisocyanate, diphenylmethane diisocyanate, phenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc., can be used as the curing agent.

[0036] (Surface protective layer)

[0037] The surface protective layer 14 is a layer formed on the adhesive layer 13, and is set up to give the decorative piece 10 functions such as weather resistance, scratch resistance, stain resistance, and design.

[0038] As the material for the surface protective layer 14, considering scratch resistance, weather resistance, and durability, a mixture of an ionizing radiation-curing resin and an isocyanate-curing acrylic resin composition can be used, for example. Regarding scratch resistance, the hardness of the surface protective layer 14 according to the pencil hardness test of JIS K 5600 is preferably B or higher. Furthermore, as the ionizing radiation-curing resin, a composition in which at least one of the following prepolymers, oligomers, and monomers is a main component can be used, wherein the prepolymer, oligomer, and monomer contain polymerizable unsaturated bonds such as (meth)acryloyl groups that have the property of undergoing a crosslinking reaction upon irradiation by ionizing radiation. As the ionizing radiation, electron beams or ultraviolet light can be used, for example. Additives such as polymerization initiators and sensitizers can also be added to the ionizing radiation-curing resin as needed.

[0039] As prepolymers or oligomers with polymerizable unsaturated bonds, examples include: melamine (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polyol (meth)acrylate. Additionally, as monomers, examples include: monofunctional monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, hydroxyethyl (meth)acrylate, and glycidyl (meth)acrylate; difunctional monomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, and hexanediol diacrylate; and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0040] As an isocyanate-cured acrylic resin composition, for example, a reaction product obtained by using an acrylic resin composition as the main agent and a polyisocyanate as the curing agent can be used. As an acrylic resin composition, for example, an acrylic polyol compound can be used. As an acrylic polyol compound, for example, an acrylic polymer compound having hydroxyl groups in its side chain can be used, which is obtained by copolymerizing common acrylic monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate with monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate, and polymerizable monomers such as styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl butyrate, vinyl tert-carbonate, ethyl vinyl ether, acrylonitrile, and methacrylonitrile, which are copolymerizable as needed.

[0041] In addition, isocyanate prepolymers such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), phenyl dimethyl diisocyanate (XDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated phenyl dimethyl diisocyanate (hydrogenated XDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) can be used, considering weather resistance, yellowing resistance, and production efficiency. That is, isocyanurate-type products based on HDI, i.e., HDI isocyanurate derivatives of HDI, can be used. Furthermore, urethane bonds can be used as side chains of the isocyanate prepolymer, for example, to impart flexibility to the surface protective layer 14.

[0042] Depending on the requirements, the surface protective layer 14 can be combined with various additives such as ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst traps, colorants, light scattering agents, and gloss modifiers.

[0043] There is no particular limitation on the method of forming the surface protective layer 14. The above-mentioned material is coated with the liquefied material by conventional methods such as gravure coating, micro-gravure coating, comma coating, doctor blade coating, and mold coating, and then cured by a method suitable for the material, such as thermosetting or ultraviolet curing, thereby forming the surface protective layer 14.

[0044] In addition, a surfactant is added to the surface protective layer 14. The surfactant includes at least one of cationic surfactants, amphoteric surfactants, or nonionic surfactants. By adding a surfactant, the compatibility between the silver-based antiviral agent and the surface protective layer in the adhesive becomes good, thereby obtaining a decorative sheet that suppresses concentration deviations caused by precipitation of the antiviral agent in the coating.

[0045] Furthermore, the thickness of the surface protective layer 14 is preferably in the range of 3 μm to 15 μm. If the thickness of the surface protective layer 14 is 3 μm or more, the scratch resistance is improved. If the thickness of the surface protective layer 14 is 15 μm or less, more resin material than required is not needed, thus reducing costs.

[0046] [Antiviral agents]

[0047] The surface protective layer 14 contains antiviral agents that enhance antiviral activity.

[0048] Silver-based materials are preferred as antiviral agents. As antiviral agents, inorganic antibacterial agents such as antibacterial zeolite, antibacterial apatite, and antibacterial zirconium oxide, formed by incorporating any one of the metal ions (silver, copper, or zinc) into inorganic compounds such as zeolite, apatite, and zirconium oxide, can be used. Additionally, pyridine-2-thiol-zinc pyridine, 2-(4-thiazolyl)-benzimidazole, 10,10-oxobisphenoxarium, organic nitrogen-sulfur halogen compounds, and pyridine-2-thiol oxides can also be used. However, silver-based antiviral agents exhibit superior antiviral efficacy.

[0049] In addition, antiviral agents can be composed of silver-based materials loaded onto inorganic materials.

[0050] The amount of antiviral agent added to the surface protective layer 14 is preferably in the range of 0.2 parts by weight to 10 parts by weight. When the amount of antiviral agent added is 0.2 parts by weight or more, the antiviral agent works effectively, and the antiviral activity is improved. When the amount of antiviral agent added is 10 parts by weight or less, the wound resistance is improved.

[0051] The average particle size of the antiviral agent is preferably 0.5 to 2 times the thickness of the surface protective layer 14. That is, when the average particle size of the antiviral agent is set to... When the thickness of the surface protective layer is set to D... The relationship holds true. When the average particle size of the antiviral agent is more than 0.5 times but less than 2 times that of the surface protective layer 14, the antiviral activity becomes good due to the increased contact area with the antiviral agent and the increased surface area of ​​the antiviral agent itself.

[0052] Furthermore, the average particle size of the antiviral agent is preferably 1 μm or more and 10 μm or less. When the average particle size of the antiviral agent is 1 μm or more, the contact area between the surface protective layer 14 and the antiviral agent is increased, resulting in better antiviral properties. When the average particle size of the antiviral agent is 10 μm or less, the damage resistance is improved.

[0053] Furthermore, it is preferable that the antiviral agent has multiple peak values ​​in its particle size. Specifically, the peak values ​​of the antiviral agent's particle size preferably include a first peak value in the range of 1 μm to 5 μm and a second peak value in the range of 5 μm to 10 μm. Here, the second peak value of the antiviral agent's particle size is set to a value greater than the first peak value. By having multiple peak values ​​in the antiviral agent's particle size, the packing density of the antiviral agent is further increased, thereby allowing more antiviral agent to be added. Therefore, the contact area with the antiviral agent is increased, the surface area of ​​the antiviral agent itself is also increased, and the antiviral activity is improved.

[0054] The surface protective layer 14 contains a nucleating agent that improves the crystallinity of the resin material. In this embodiment, the nucleating agent is added to the resin material in the form of nucleating agent vesicles encapsulated within the outer membrane.

[0055] [Nucleating agent]

[0056] The surface protective layer 14 contains nano-sized nucleating agents. The nano-sized nucleating agents are preferably added to the polypropylene resin in the form of nucleating agent vesicles encapsulated within vesicles having a single-layer outer membrane. Furthermore, in this embodiment, the nucleating agent in the resin constituting the surface protective layer 14 can be encapsulated within vesicles with a portion of the nucleating agent exposed. Because the surface protective layer 14 contains nucleating agents, crystallinity can be increased, thereby improving the scratch resistance of the decorative sheet 10.

[0057] The average particle size of the nano-sized nucleating agent is preferably less than half of the wavelength region of visible light. Specifically, since the wavelength region of visible light is from 400 nm to 750 nm, the average particle size is preferably less than 375 nm.

[0058] Because of the extremely small particle size of nano-sized nucleating agents, the number and surface area of ​​nucleating agents per unit volume increase inversely proportional to the cube of the particle diameter. As a result, the distance between the nucleating agent particles becomes closer, so when crystal growth begins from the surface of one nucleating agent particle added to the resin, the growing end of the crystal immediately contacts the growing ends of crystals growing from the surfaces of other nucleating agent particles adjacent to it. The growth of these crystal ends is hindered, thus halting the growth of each individual crystal. Therefore, the average particle size of spherulites in the crystalline portion of the crystalline resin can be reduced, for example, to below 1 μm. Consequently, stress concentration between spherulites generated during bending processing can be effectively dispersed while forming a highly crystalline, high-hardness resin film, thus achieving a resin film that suppresses cracking and whitening during bending processing.

[0059] When only nucleating agents are added, the particle size of the nucleating agents in the resin increases due to secondary aggregation. On the other hand, when nucleating agent vesicles are added, the dispersibility in the resin is improved, and therefore the number of crystal nuclei increases significantly relative to the amount of nucleating agent added compared to the case of adding nucleating agents alone. As a result, the average particle size of spherulites in the crystalline part of the resin becomes smaller, which can suppress cracking and whitening during bending processing. Thus, by adding nucleating agent vesicles, crystallinity can be further improved, thereby achieving a better balance between improving elastic modulus and processability.

[0060] The surface protective layer 14 is formed, for example, of a resin material in which a nucleating agent is preferably added in the range of 0.05 parts by mass to 0.5 parts by mass, more preferably 0.1 parts by mass to 0.3 parts by mass, relative to 100 parts by mass of polypropylene resin, which is the main component. When using nucleating agent vesicles, the amount of nucleating agent added to the resin material is the amount calculated as the amount of nucleating agent in the nucleating agent vesicles. When the amount of nucleating agent added is less than 0.05 parts by mass, the crystallinity of the polypropylene cannot be sufficiently increased, and thus the scratch resistance of the surface protective layer 14 may not be sufficiently improved. Furthermore, when the amount of nucleating agent added exceeds 0.5 parts by mass, due to the excessive number of crystal nuclei, the growth of spherulites in the polypropylene is hindered, resulting in insufficient improvement in the crystallinity of the polypropylene, and thus the scratch resistance of the surface protective layer 14 may not be sufficiently improved.

[0061] Here, "main component" refers to resin material that accounts for more than 50% by mass of the resin material constituting the surface protective layer 14.

[0062] In addition, methods for nano-sized nucleating agents include, for example, solid-phase methods that obtain nano-sized particles by mechanically pulverizing the nucleating agent; liquid-phase methods that synthesize or crystallize nano-sized particles in the nucleating agent or a solution containing the nucleating agent; and gas-phase methods that synthesize or crystallize nano-sized particles from the nucleating agent or a gas / vapor composed of the nucleating agent. Examples of solid-phase methods include ball mills, bead mills, rod mills, colloid mills, conical mills, disc mills, hammer mills, and jet mills. Examples of liquid-phase methods include crystallization, co-precipitation, sol-gel methods, liquid-phase reduction methods, and hydrothermal synthesis methods. Examples of gas-phase methods include electric furnace methods, chemical flame methods, laser methods, and thermal plasma methods.

[0063] Supercritical reverse-phase evaporation is a preferred method for nano-sized nucleating agents. Supercritical reverse-phase evaporation involves using carbon dioxide in a supercritical state or above the critical point at temperature or pressure conditions to create capsules (nanoscale vesicles) containing the target substance. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state above the critical temperature (30.98℃) and critical pressure (7.3773±0.0030MPa). Carbon dioxide in a temperature or pressure condition above the critical point refers to carbon dioxide where only the temperature or only the pressure exceeds the critical conditions.

[0064] Furthermore, as a specific nano-sizing process utilizing supercritical reverse-phase evaporation, firstly, an emulsion of supercritical carbon dioxide and an aqueous phase is generated by injecting and stirring a mixed fluid of supercritical carbon dioxide, phospholipids as the outer membrane forming substance, and a nucleating agent as the inner encapsulation substance. Next, by depressurization, the carbon dioxide expands / evaporates, causing a phase change and generating nanocapsules (nanovesicles) in which phospholipids cover the surface of the nucleating agent particles as a single-layer film. By using this supercritical reverse-phase evaporation method, unlike traditional encapsulation methods where the outer membrane at the surface of the nucleating agent particles becomes a multi-layer film, single-layer membrane capsules can be easily generated, thus allowing for the preparation of capsules with smaller diameters.

[0065] It should be noted that nucleating agent vesicles can be prepared by methods such as the Bangham method, extrusion method, hydration method, surfactant dialysis method, reverse phase evaporation method, freeze-dissolution method, and supercritical reverse phase evaporation method. Among these, the supercritical reverse phase evaporation method is particularly preferred for preparing nucleating agent vesicles.

[0066] The outer membrane of the nucleating agent vesicle is, for example, composed of a single-layer membrane. Furthermore, this outer membrane is, for example, composed of a substance containing biological lipids such as phospholipids.

[0067] In this specification, nucleating agent vesicles whose outer membrane is composed of bio-lipids such as phospholipids are referred to as nucleating agent liposomes.

[0068] Phospholipids that make up the outer membrane include, for example, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and other glycerophospholipids; sphingomyelin, ceramide phosphoethanolamine, ceramide phosphorylglycerol, and other sphingomyelins.

[0069] Other substances that form the outer membrane of vesicles include, for example, nonionic surfactants, or mixtures thereof with cholesterol or triglycerides, and other dispersants. Among these, nonionic surfactants include, for example, one or more of the following: polyglycerol ethers, dialkyl glycerols, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ethers, polyoxyethylene dehydrated sorbitol fatty acid esters, dehydrated sorbitol fatty acid esters, polyoxyethylene polyoxypropylene copolymers, polybutadiene-polyoxyethylene copolymers, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymers, polyethylene oxide-polyethylethylene copolymers, and polyoxyethylene-polycaprolactam copolymers. Cholesterols include, for example, cholesterol, α-cholesterol, β-cholesterol, cholesterol, sterol (5,24-cholestadien-3β-ol), sodium cholate, or cholecalciferol.

[0070] Alternatively, the outer membrane of the liposome can also be formed from a mixture of phospholipids and a dispersant. In the decorative sheet 10 of this embodiment, it is preferable to make the nucleating agent vesicles into free radical scavenging liposomes having an outer membrane composed of phospholipids. By making the outer membrane composed of phospholipids, the compatibility between the resin material, which is the main component of the decorative sheet 10, and the vesicles can be improved.

[0071] There are no particular limitations on the nucleating agent; any substance that serves as the starting point for crystallization during resin crystallization is acceptable. Examples of nucleating agents include: phosphate metal salts, benzoic acid metal salts, pimecrolic acid metal salts, rosin metal salts, benzyl sorbitol, quinacridone, sodium oleate, phthalocyanine blue, and talc. Sodium oleate is particularly preferred. Furthermore, to maximize the nano-sizing effect, non-molten phosphate metal salts, benzoic acid metal salts, pimecrolic acid metal salts, and rosin metal salts that offer good transparency can also be used. However, if nano-sizing can make the material itself transparent, colored quinacridone, phthalocyanine blue, and talc can also be used. Additionally, for non-molten nucleating agents, molten benzyl sorbitol can be appropriately mixed in.

[0072] <Effects of the first embodiment>

[0073] The decorative piece 10 involved in this embodiment has the following effects.

[0074] (1) The decorative sheet 10 of this embodiment contains an antiviral agent and a nucleating agent in its surface protective layer.

[0075] Based on this composition, both higher antiviral activity and higher damage resistance can be achieved.

[0076] (2) In the decorative sheet 10 of this embodiment, the amount of antiviral agent added relative to the surface protective layer 14 is more than 0.2 parts by mass and less than 10 parts by mass.

[0077] According to this composition, the antiviral effect is improved by including more than 0.2 parts by mass of antiviral agent, and high wound resistance can be obtained by setting the antiviral agent to less than 10 parts by mass.

[0078] <Second Implementation>

[0079] (Composition of decorative pieces)

[0080] use Figure 2 The decorative sheet according to the second embodiment of this disclosure will be described. Figure 2 This is a cross-sectional view illustrating a configuration example of the decorative sheet 20 according to the second embodiment of this disclosure.

[0081] The decorative sheet 20 has a colored pattern layer 12, an adhesive layer 13, a thermoplastic resin layer 25, and a surface protective layer 14 sequentially stacked on one side of the substrate sheet 11.

[0082] That is, the decorative sheet 20 differs from the decorative sheet 10 of the first embodiment in that it has a thermoplastic resin layer 25. In addition, the decorative sheet 20 contains an antiviral agent in at least the surface protective layer 14, and contains a nucleating agent in at least one of the surface protective layer 14 or the thermoplastic resin layer 25, which differs from the decorative sheet 10 of the first embodiment.

[0083] The thermoplastic resin layer 25 will be described below. It should be noted that the other layers (substrate sheet 11, colored pattern layer 12, adhesive layer 13, and surface protective layer 14) have the same structure as the layers of the decorative sheet 10, so they will not be described.

[0084] (Thermoplastic resin layer)

[0085] like Figure 2 As shown, the thermoplastic resin layer 25 is a layer formed between the adhesive layer 13 and the surface protective layer 14.

[0086] The thickness of the thermoplastic resin layer 25 is preferably 50 μm to 110 μm, more preferably 70 μm to 95 μm. When the thickness of the thermoplastic resin layer 25 is 70 μm or more, the thermoplastic resin layer 25 becomes sufficiently resistant to damage from shoe heels or small stones. In addition, when the thickness of the thermoplastic resin layer 25 is 110 μm or less, the flexibility of the decorative piece 10 will not be excessively high, and even if the floor material to which the decorative piece 10 is attached is not flat, it can be installed while adhering closely to the floor material.

[0087] [Resin Material]

[0088] As the resin material constituting the thermoplastic resin layer 25, the same thermoplastic resin as the substrate sheet 11 can be used. There are no particular limitations on the thermoplastic resin; for example, the following polyolefin resins can be used: polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, etc.; olefin copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylate copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralizer (ionomer), etc.; and polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanediol copolymer, polyethylene terephthalate. Polyester resins such as esters, polyarylates, and polycarbonates; acrylic resins such as poly(meth)acrylonitrile, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)butyl acrylate, and polyacrylamide; polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon; styrene resins such as polystyrene, AS resin, and ABS resin; vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl alcohol acetal, and polyvinyl alcohol butyral; fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, and ethylene-perfluoroalkyl vinyl ether copolymer; or mixtures, copolymers, composites, and laminates of two or more of these.

[0089] Here, many thermoplastic resins are listed as suitable for use in the thermoplastic resin layer 25. However, given the high level of public concern about environmental issues in recent years, non-halogen thermoplastic resins are preferred over chlorine-containing (halogen) thermoplastic resins such as polyvinyl chloride resin. In particular, considering various physical properties, processability, versatility, and economic factors, polyolefin resins or polyester resins (amorphous or biaxially stretched) are the most preferred non-halogen thermoplastic resins.

[0090] As a polyolefin resin, it is appropriate to select from the many types listed above, depending on the intended use of the decorative sheet 10. In particular, polypropylene resins, i.e., homopolymers or copolymers with propylene as the main component, are most suitable for general applications. For example, homopolymers, atactic polypropylene resins, block polypropylene resins, etc., can be used alone or appropriately combined, or resins obtained by further appropriately combining atactic polypropylene can be used. In addition, copolymers containing olefin monomers other than propylene can also be used. For example, propylene-α-olefin copolymers that have a polypropylene crystalline portion and contain 15 mol% or more of α-olefins with 2 to 20 carbon atoms other than propylene, preferably one or two or more comonomers selected from ethylene, butene-1, 4-methylpentene-1, hexene-1, or octene-1, can be used. In addition, modifiers such as low-density polyethylene, ethylene-α-olefin copolymers, ethylene-propylene copolymer rubbers, ethylene-propylene-nonconjugated diene copolymer rubbers, styrene-butadiene copolymers, or their hydrogenates, which are commonly used for softening polypropylene resins, can be appropriately added.

[0091] Depending on the needs, for example, one or more additives selected from colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, mildew inhibitors, friction reducers, light scattering agents, and gloss modifiers may be added to the thermoplastic resin layer 25. It should be noted that the thermoplastic resin layer 25 preferably has a degree of transparency (colorless transparent, colored transparent, translucent) that allows the pattern of the patterned layer 12 to be seen from the surface (top) of the decorative sheet 10.

[0092] Furthermore, the thermoplastic resin layer 25 may contain an antiviral agent that enhances antiviral properties, similar to the surface protective layer 14. By including an antiviral agent in the surface protective layer 14, antiviral properties can be maintained at the outermost surface of the decorative sheet. By including antiviral agents in both the thermoplastic resin layer 25 and the surface protective layer 14, antiviral properties are maintained even if the thermoplastic resin layer 25 is exposed due to wear of the surface protective layer 14. Therefore, it is more preferable to include antiviral agents in both the surface protective layer 14 and the thermoplastic resin layer 25. It should be noted that, since the antiviral agent has the same composition as the antiviral agent included in the surface protective layer 14 of the decorative sheet 10, a description is omitted.

[0093] In this embodiment, at least one of the surface protective layer 14 or the thermoplastic resin layer 25 contains a nucleating agent. By including a nucleating agent in the surface protective layer 14, excellent scratch resistance and abrasion resistance are achieved, suppressing damage caused by heels or small stones during heavy walking. Furthermore, by including a nucleating agent in the thermoplastic resin layer 25, the overall strength of the decorative sheet can be maintained even if the surface protective layer 14 wears down and the thermoplastic resin layer 25 is exposed. Additionally, by including nucleating agents in both the surface protective layer 14 and the thermoplastic resin layer 25, the scratch resistance, impact resistance, and caster resistance required for flooring material performance are improved. Therefore, it is more preferable that both the surface protective layer 14 and the thermoplastic resin layer 25 contain nucleating agents. It should be noted that the nucleating agent has the same composition as the nucleating agent included in the surface protective layer 14 of the decorative sheet 10, so a description is omitted.

[0094] <Effects of the Second Embodiment>

[0095] In addition to the effects of the first embodiment, the decorative piece 20 involved in this embodiment also has the following effects.

[0096] (3) The decorative sheet 20 of this embodiment has a thermoplastic resin layer 25.

[0097] This structure can improve the overall strength of the decorative panel and provide cushioning.

[0098] <Third Implementation>

[0099] (Composition of decorative pieces)

[0100] use Figure 3 The decorative sheet according to the third embodiment of this disclosure will be described. Figure 3 This is a cross-sectional view illustrating a configuration example of the decorative sheet 30 according to the third embodiment of this disclosure.

[0101] The decorative sheet 30 has a colored pattern layer 12, an adhesive layer 13, a thermoplastic resin layer 35, and a surface protective layer 34 sequentially stacked on one side of the substrate sheet 11.

[0102] That is, the decorative sheet 20 has a surface protective layer 34 instead of the surface protective layer 14 and has a thermoplastic resin layer 35, which differs from the decorative sheet 10 according to the first embodiment. In addition, the surface protective layer 34 or the thermoplastic resin layer 35 of the decorative sheet 30 has nanoparticles instead of nucleating agents, which also differs from the decorative sheet 10.

[0103] The surface protective layer 34 and the thermoplastic resin layer 35 will be described below. It should be noted that the other layers (substrate sheet 11, colored pattern layer 12, and adhesive layer 13) are constructed in the same way as the layers of the decorative sheet 10, and therefore will not be described.

[0104] As inorganic particles, examples include microparticles composed of inorganic materials such as silicon dioxide, glass, alumina, titanium dioxide, zirconium oxide, calcium carbonate, and barium sulfate at the nanoscale.

[0105] The surface protective layer 34 is formed, for example, of a resin material in which inorganic particles are added in an amount ranging from 0.1 parts by mass to 30 parts by mass relative to 100 parts by mass of resin material. When the amount of inorganic particles added is 0.1 parts by mass or more, sufficient scratch resistance can be achieved. When the amount of inorganic particles added is 30 parts by mass or less, degradation of transparency can be prevented, and material reduction can be achieved.

[0106] In this embodiment, at least one of the surface protective layer 34 or the thermoplastic resin layer 35 comprises an inorganic material. This increases the strength of the decorative piece 30.

[0107] <Effects of the Third Embodiment>

[0108] The decorative piece 30 involved in this embodiment has the same effect as the first and second embodiments.

[0109] <Fourth Implementation>

[0110] use Figure 4 The decorative material involved in the fourth embodiment of this disclosure will be described. Figure 4 This is a cross-sectional view illustrating a configuration example of the decorative material 40 according to the fourth embodiment of this disclosure.

[0111] (Decorative materials)

[0112] The decorative material 40 has a colored pattern layer 12, an adhesive layer 13 and a surface protective layer 14 stacked sequentially on one side of the substrate sheet 11, and a primer layer 46 and a substrate 47 are provided on the other side of the substrate sheet 11.

[0113] That is, the decorative material 40 has a primer layer 46 and a substrate 47, which is different from the decorative sheet 10 involved in the first embodiment.

[0114] The primer layer 46 and the substrate 47 will be described below. It should be noted that the other layers (substrate sheet 11, colored pattern layer 12, adhesive layer 13, and surface protective layer 14) are constructed in the same way as the layers of the decorative sheet 10, and therefore will not be described.

[0115] (Primer layer)

[0116] The primer layer 46 is applied as needed to improve the adhesion between the substrate on the opposite side of the colored pattern layer 12 in the base sheet 11 of the decorative sheet 10 and the adhesive used for bonding. For example, when the substrate is made of wood, adhesives such as vinyl acetate emulsions and two-component curing urethanes are used as adhesives, so the primer layer 46 is preferably designed with a resin that matches these adhesives. For example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymers, vinyl chloride-vinyl acetate copolymers, polyester-based, etc., can be used. Two-component curing urethane primers made of polyester polyols and polyisocyanates are particularly preferred. In addition, for example, when inorganic powders such as silica, barium sulfate, and calcium carbonate are added, it is effective in preventing adhesion during winding and storage and improving the adhesive force generated by the anchoring action.

[0117] (Substrate)

[0118] As the substrate 47, a wood-based substrate or a metal-based substrate can be used. Examples of wood-based substrates include: wood veneer, plywood, engineered wood, particleboard, medium-density fiberboard, and hardboard. By forming the substrate 47, a decorative material 40 can be provided that can inhibit damage caused by heels or small stones during heavy walking.

[0119] It should be noted that in this embodiment, a primer layer 46 and a substrate 47 are adhered to the decorative sheet 10, but decorative sheet 20 or decorative sheet 30 can also be used to replace decorative sheet 10 to form decorative material.

[0120] <Effects of the Fourth Implementation>

[0121] In addition to the effects of the first to third embodiments, the decorative material 40 involved in this embodiment also has the following effects.

[0122] (4) The decorative material 40 of this embodiment has a primer layer 46 and a substrate 47.

[0123] This design can suppress injuries caused by heels or small stones during heavy walking.

[0124] Example

[0125] The present disclosure will be further described in detail below through embodiments, but the present disclosure is not limited to the embodiments in any way.

[0126] <Example 1>

[0127] First, a colored polyethylene resin (PE) sheet is prepared as the substrate. The thickness of the substrate is set to 55 μm. Next, a corona discharge treatment is performed on one side (surface) of the substrate. Then, a urethane-based printing ink is coated onto the corona-treated surface of the substrate to form a patterned layer. Next, a urethane-based adhesive is coated onto the surface of the formed patterned layer to form an adhesive layer.

[0128] Next, a polypropylene (PP) film is deposited on the surface of the formed adhesive layer to form a thermoplastic resin layer. The thickness of the thermoplastic resin layer is set to 100 μm. The following describes a detailed method for preparing a resin composition with a thermoplastic resin layer containing a nucleating agent vesicled by supercritical reverse-phase evaporation. First, in the vesicledization treatment method using a nucleating agent via supercritical reverse-phase evaporation, 100 parts by weight of methanol, 82 parts by weight of a phosphate metal salt nucleating agent (ADK STAB NA-11, manufactured by ADEKA), and 5 parts by weight of phosphatidylcholine constituting the vesicle outer membrane are placed in a high-pressure stainless steel container maintained at 60°C and sealed. Carbon dioxide is injected to achieve a supercritical state at a pressure of 20 MPa, and then 100 parts by weight of deionized water is injected while vigorously stirring and mixing. The mixture is stirred for 15 minutes while maintaining the temperature and pressure inside the container at a supercritical state, and then the carbon dioxide is removed to restore atmospheric pressure, thereby obtaining the vesicled nucleating agent. In practice, when forming a transparent resin sheet as a thermoplastic resin layer, a resin is extruded using a melt extruder by adding the following substances to a highly crystalline homopolymer polypropylene resin with a five-component ratio of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230°C), and a molecular weight distribution MWD (Mw / Mn) of 2.3: 500 PPM of a hindered phenolic antioxidant (Irganox 1010: manufactured by BASF), 2000 PPM of a benzotriazole UV absorber (Tinuvin 328: manufactured by BASF), 2000 PPM of a hindered amine light stabilizer (Chimassorb 944: manufactured by BASF), and 1000 PPM of a nucleating agent obtained by nano-sizing via the supercritical reverse-phase evaporation method described above. This yields a resin sheet made of highly crystalline polypropylene with a thickness of 100 μm, which is used as the thermoplastic resin layer.

[0129] Next, a surface protective layer is formed by coating the surface of the thermoplastic resin layer with a mixture of an ionizing radiation-curable resin and an isocyanate-curable acrylic resin composition with acrylic polyol as the main agent and polyisocyanate as the curing agent, and then curing. At this time, the ratio of the isocyanate-curable acrylic resin composition to the total mass of the surface protective layer is set to 30 parts by mass. The amount of polyisocyanate added is 10 parts by mass relative to the acrylic resin composition (NCO / OH = 1.0). Additionally, as an antiviral agent, 0.2 parts by mass of a silver-based inorganic additive (manufactured by Taisho Technos Co., Ltd., BIOSAIDO TB-B100) with an average particle size of 5 μm is added to the acrylic resin composition. It should be noted that the active ingredient of the antiviral agent is loaded with an inorganic material. At this time, the first peak particle size of the antiviral agent is 3 μm, and the second peak particle size is 7 μm.

[0130] In addition, in the acrylic resin composition, 0.01 parts by weight of nucleating agent vesicles, which are formed by encapsulating nano-sized nucleating agents in vesicles with a single-layer outer membrane, are added relative to the total mass of the acrylic resin composition. Here, the vesicle formation using the supercritical reverse-phase evaporation method will be described. First, 100 parts by weight of methanol, 70 parts by weight of sodium oleate as a dispersant, and 5 parts by weight of phosphatidylcholine as a substance constituting the outer membrane of the vesicle are placed in a high-pressure stainless steel container maintained at 60°C and sealed. Carbon dioxide is injected into the container to achieve a pressure of 20 MPa to achieve a supercritical state. Then, 100 parts by weight of deionized water are injected while vigorously stirring in the container. While maintaining the temperature and pressure at a supercritical state, the mixture is further stirred and mixed for 15 minutes. Then, the carbon dioxide is removed from the container to restore atmospheric pressure, thereby obtaining liposomes with an outer membrane composed of phospholipids encapsulating a dispersant. It should be noted that when the outer membrane of the vesicle is a dispersant or similar substance, it is obtained by using the above-mentioned dispersant instead of phosphatidylcholine.

[0131] Here, the thickness of the surface protective layer is set to 10 μm. At this point, the average particle size of the antiviral agent is 0.5 times the thickness of the surface protective layer.

[0132] As described above, the decorative sheet of Example 1 was fabricated. It should be noted that the thickness of the decorative sheet is 140 μm.

[0133] <Example 2>

[0134] The amount of antiviral agent added was changed to 5 parts by weight. Otherwise, the decorative sheet of Example 2 was prepared using the same method as in Example 1.

[0135] <Example 3>

[0136] The amount of antiviral agent added was changed to 10 parts by weight. Otherwise, the decorative sheet of Example 3 was prepared using the same method as in Example 1.

[0137] <Example 4>

[0138] The average particle size of the antiviral agent was changed to 0.1 μm. Otherwise, the decorative sheet of Example 4 was prepared using the same method as in Example 2.

[0139] <Example 5>

[0140] The average particle size of the antiviral agent was changed to 1 μm. Otherwise, the decorative sheet of Example 5 was prepared using the same method as in Example 2.

[0141] <Example 6>

[0142] The average particle size of the antiviral agent was changed to 10 μm. Otherwise, the decorative sheet of Example 6 was prepared using the same method as in Example 2.

[0143] <Example 7>

[0144] The average particle size of the antiviral agent was changed to 20 μm. Otherwise, the decorative sheet of Example 7 was prepared using the same method as in Example 2.

[0145] <Example 8>

[0146] The first peak value of the antiviral agent particle size was changed to 0.1 μm. Otherwise, the decorative sheet of Example 8 was prepared using the same method as in Example 2.

[0147] <Example 9>

[0148] The first peak value of the antiviral agent particle size was changed to 1 μm. Otherwise, the decorative sheet of Example 9 was prepared using the same method as in Example 2.

[0149] <Example 10>

[0150] The first peak value of the antiviral agent particle size was changed to 5 μm. Otherwise, the decorative sheet of Example 10 was prepared using the same method as in Example 2.

[0151] <Example 11>

[0152] The first peak value of the antiviral agent particle size was changed to 6 μm. Otherwise, the decorative sheet of Example 11 was prepared using the same method as in Example 2.

[0153] <Example 12>

[0154] The second peak value of the antiviral agent particle size was changed to 4 μm. Otherwise, the decorative sheet of Example 12 was prepared using the same method as in Example 2.

[0155] <Example 13>

[0156] The second peak value of the antiviral agent particle size was changed to 5 μm. Otherwise, the decorative sheet of Example 13 was prepared using the same method as in Example 2.

[0157] <Example 14>

[0158] The second peak value of the antiviral agent particle size was changed to 10 μm. Otherwise, the decorative sheet of Example 14 was prepared using the same method as in Example 2.

[0159] <Example 15>

[0160] The second peak value of the antiviral agent particle size was changed to 20 μm. Otherwise, the decorative sheet of Example 15 was prepared using the same method as in Example 2.

[0161] <Example 16>

[0162] The first peak value of the antiviral agent particle size was changed to 0.1 μm, and the second peak value was changed to 4 μm. Otherwise, the decorative sheet of Example 16 was prepared using the same method as in Example 2.

[0163] <Example 17>

[0164] The first peak value of the antiviral agent particle size was changed to 10 μm, and the second peak value was changed to 20 μm. Otherwise, the decorative sheet of Example 17 was prepared using the same method as in Example 2.

[0165] <Example 18>

[0166] The thickness of the surface protective layer was changed to 1 μm. Otherwise, the decorative sheet of Example 18 was produced using the same method as in Example 2.

[0167] <Example 19>

[0168] The thickness of the surface protective layer was changed to 3 μm. Otherwise, the decorative sheet of Example 19 was produced using the same method as in Example 2.

[0169] <Example 20>

[0170] The thickness of the surface protective layer was changed to 15 μm. Otherwise, the decorative sheet of Example 20 was produced using the same method as in Example 2.

[0171] <Example 21>

[0172] The thickness of the surface protective layer was changed to 25 μm. Otherwise, the decorative sheet of Example 21 was produced using the same method as in Example 2.

[0173] <Example 22>

[0174] Untreated nucleating agents were used in the surface protective layer, instead of nucleating agent vesicles formed by encapsulating nano-sized nucleating agents in vesicles with a single outer membrane. Otherwise, the decorative sheet of Example 22 was prepared using the same method as in Example 2.

[0175] <Example 23>

[0176] 0.01 parts by mass of inorganic particles were added to the surface protective layer instead of nucleating agent vesicles. Otherwise, the decorative sheet of Example 23 was prepared using the same method as in Example 2.

[0177] <Example 24>

[0178] In the surface protective layer, the addition of a nucleating agent was omitted. Additionally, in the thermoplastic resin layer, 0.01 parts by weight of a nucleating agent vesicle, which consists of nano-sized nucleating agents encapsulated within vesicles having a single-layer outer membrane, was added relative to the total mass of the thermoplastic resin layer. Otherwise, the decorative sheet of Example 24 was prepared using the same method as in Example 2.

[0179] <Example 25>

[0180] An untreated nucleating agent was used in the thermoplastic resin layer, instead of nucleating agent vesicles formed by encapsulating nano-sized nucleating agents in vesicles with a single-layer outer membrane. Otherwise, the decorative sheet of Example 25 was produced using the same method as in Example 24.

[0181] <Example 26>

[0182] 0.01 parts by weight of inorganic particles were added to the thermoplastic resin layer instead of nucleating agent vesicles. Otherwise, the decorative sheet of Example 26 was produced using the same method as in Example 24.

[0183] <Example 27>

[0184] In the thermoplastic resin layer, 0.01 parts by weight of nucleating agent vesicles, which consist of nano-sized nucleating agents encapsulated in vesicles having a single-layer outer membrane, were added relative to the total mass of the thermoplastic resin layer. Otherwise, the decorative sheet of Example 27 was prepared using the same method as in Example 2.

[0185] <Comparative Example 1>

[0186] The addition of antiviral agents was omitted from the surface protective layer. Otherwise, the decorative sheet of Comparative Example 1 was produced using the same method as in Example 28.

[0187] <Comparative Example 2>

[0188] The amount of antiviral agent added was changed to 0.1 parts by weight. Otherwise, the decorative sheet of Comparative Example 2 was prepared by the same method as Comparative Example 1.

[0189] <Comparative Example 3>

[0190] The nucleating agent was omitted from the surface protective layer. Otherwise, the decorative sheet of Comparative Example 3 was prepared using the same method as Comparative Example 2.

[0191] <Comparative Example 4>

[0192] The amount of antiviral agent added was changed to 11 parts by weight. Otherwise, the decorative sheet of Comparative Example 4 was prepared by the same method as Comparative Example 1.

[0193] <Evaluation and Judgment>

[0194] The antiviral properties and damage resistance of the decorative sheets obtained in Examples 1 to 27 and Comparative Examples 1 to 4 were evaluated using the following methods.

[0195] <Evaluation>

[0196] [Antiviral properties]

[0197] Antiviral tests were performed on the decorative films of Examples 1-27 and Comparative Examples 1-4 according to ISO 21702. The test samples were placed in sterile petri dishes, and 0.4 mL of virus solution was inoculated onto the samples. The virus solution used was an enveloped virus (influenza virus). Then, a 40 mm square polyethylene film was placed over the samples. The petri dishes were covered, and the virus was inoculated onto the samples at 25°C / 90% or higher humidity. After a predetermined time, 10 mL of SCDLP medium was injected into the petri dishes to elute the virus. The viral infection titer of the eluent was determined using the plaque assay.

[0198] <Determination of Viral Infection Potency (Plaque Method)>

[0199] Host cells were cultured in a monolayer in 6-well plates, and 0.1 mL of a step-diluted elution buffer was inoculated into each well. The plates were incubated at 5% CO2 / 37°C for 1 hour to allow virus adsorption onto the cells. Agar medium was then added to the 6-well plates, and the plates were incubated for another 2–3 days. After incubation, the cells were fixed / stained, and the number of plaques formed was measured.

[0200] <Calculation of Viral Infection Titer>

[0201] Calculate each 1cm according to the following formula. 2 Viral infection titer of the sample.

[0202] V=(10×C×D×N) / A

[0203] V: per 1cm 2 Viral infection titer of the sample (PFU / cm) 2 )

[0204] C: Number of etch spots measured

[0205] D: Dilution factor of the hole used to measure the etching pit

[0206] N: SCDLP quantity

[0207] A: The contact area between the sample and the virus (the area of ​​the polyethylene film).

[0208] <Calculation of antiviral activity value>

[0209] Calculate the antiviral activity value according to the following formula.

[0210] Antiviral activity value = log(Vb) - log(Vc)

[0211] Log(Vb): The percentage of unprocessed sample per 1 cm after 24 hours. 2 Commonly used logarithmic values ​​of viral infection titer

[0212] Log(Vc): The antiviral processing sample per 1cm after 24 hours 2 Commonly used logarithmic values ​​of viral infection titer

[0213] The calculated antiviral activity value was evaluated using the following three levels: ◎, 〇, and ×.

[0214] <Evaluation Criteria>

[0215] ◎: Cases with an antiviral activity value of 3 log10 or higher

[0216] ○: Cases where the antiviral activity value is greater than 2log10

[0217] ×: Cases where the antiviral activity value is less than 2log10

[0218] [Injury Resistance]

[0219] The decorative pieces of Examples 1 to 27 and Comparative Examples 1 to 4 were subjected to a pencil hardness test as specified in JIS K5600 to confirm the degree of damage, and were evaluated using the following three levels: ◎, 〇, and ×.

[0220] <Evaluation Criteria>

[0221] ◎: No damage occurs at B level or above.

[0222] ○: No damage during 2B to 3B.

[0223] ×: Damage occurs when the level is below 4B.

[0224] The evaluation results are shown in Table 1.

[0225] [Table 1]

[0226]

[0227] As shown in Table 1, based on the evaluation results of Examples 1 to 27 and Comparative Examples 1 and 2, it can be seen that the antiviral activity is high when the amount of antiviral agent added is 0.2 parts by mass or more, as in Comparative Examples 1 and 2, compared with the case where the amount of antiviral agent added is less than 0.2 parts by mass, as in Examples 1 to 27.

[0228] Furthermore, based on the evaluation results of Examples 1 to 27 and Comparative Example 3, it can be seen that, compared with the case where no nucleating agent and inorganic particles were added to the surface protective layer and thermoplastic resin layer as in Comparative Example 3, the scratch resistance is high when nucleating agent or inorganic particles are added to the surface protective layer or thermoplastic resin layer as in Examples 1 to 27.

[0229] It should be noted that the decorative sheets and decorative materials disclosed herein are not limited to the above-described embodiments and examples, and various changes can be made without impairing the features of the invention.

[0230] Explanation of symbols

[0231] 10, 20, 30: Decorative pieces

[0232] 40: Decorative materials

[0233] 11: Substrate sheet

[0234] 12: Colored Pattern Layer

[0235] 13: Adhesive layer

[0236] 14, 34: Surface protective layer

[0237] 25, 35: Thermoplastic resin layer

[0238] 46: Primer layer

[0239] 47: Substrate

Claims

1. A decorative piece, comprising: substrate sheet, Adhesive layer, Surface protective layer, and thermoplastic resin layer, The surface protective layer contains an antiviral agent. Both the surface protective layer and the thermoplastic resin layer contain nucleating agents. The nucleating agent is added in the form of a nucleating agent vesicle encapsulated in an outer membrane. The amount of the antiviral agent added relative to the surface protective layer is more than 0.2 parts by weight and less than 10 parts by weight. The antiviral agent has multiple peak values ​​in its particle size. The peak values ​​of the particle size of the antiviral agent include: The first peak value is in the range of 1μm to 3μm, and the second peak value is in the range of 5μm to 10μm. The surface protective layer is made of a mixture of an ionizing radiation-curable resin and an isocyanate-curable acrylic resin. As the ionizing radiation-curable resin, a composition is used with at least one of the following prepolymers, oligomers, and monomers as main components, wherein the prepolymers, oligomers, and monomers contain (meth)acryloyl polymerizable unsaturated bonds that have the property of undergoing a crosslinking reaction upon irradiation by ionizing radiation.

2. The decorative piece according to claim 1, wherein, The antiviral agent is a silver-based material.

3. The decorative piece according to claim 1 or 2, wherein, The thickness of the surface protective layer is between 3 μm and 15 μm.

4. The decorative piece according to claim 1 or 2, wherein, The average particle size of the antiviral agent is more than 0.5 times and less than 2 times the thickness of the surface protective layer.

5. The decorative piece according to claim 1 or 2, wherein, The antiviral agent has an average particle size of more than 1 μm and less than 10 μm.

6. The decorative piece according to claim 1 or 2, characterized in that, The antiviral agent is loaded with inorganic materials.

7. The decorative sheet according to claim 1 or 2, wherein, The surface protective layer is further enriched with a surfactant.

8. The decorative piece according to claim 7, wherein, The surfactant comprises at least one of a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant.

9. A decorative material, characterized in that, have: Base materials for decorative materials, and The decorative sheet of any one of claims 1 to 8 is attached to the substrate for the decorative material.

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