Laminated Sheet

Abstract

To provide a laminated sheet which has a surface protective layer achieving both antiviral property and heat resistance and is used for a building material.SOLUTION: A laminated sheet 10 has a base material layer 1 and a surface protective layer 2, wherein the surface protective layer contains a resin component, a cationic polymer-based antiviral agent A, and a silver or silver zinc-based antiviral agent B.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present disclosure relates to laminated sheets. [Background technology]

[0002] In recent years, there have been outbreaks of pandemic viruses such as the novel coronavirus (COVID-19) and avian influenza. As a countermeasure, progress has been made in the development of materials that can inactivate viruses. Similarly, building materials used in everyday living spaces are also required to have the ability to inactivate viruses.

[0003] For example, Patent Document 1 discloses an antiviral vinyl chloride resin wallpaper having a polyvinyl chloride resin layer containing a polyvinyl chloride resin formed by mixing a vinyl chloride paste resin and a vinyl chloride suspension resin, and a sulfonic acid surfactant. Patent Document 2 also discloses an antiviral wallpaper having a substrate, a resin layer, and a surface treatment layer in this order, the surface treatment layer containing a resin for the surface treatment layer and a photocatalyst.

[0004] Patent Document 3 discloses a decorative sheet having a colored thermoplastic resin layer, a design layer, a transparent thermoplastic resin layer, and a surface protective layer provided at least in this order. It further discloses that the surface protective layer contains an antiviral additive in which the active ingredient is supported on an inorganic material. Patent Document 4 discloses a decorative sheet having a surface protective layer provided on a base sheet. It further discloses that the surface protective layer contains an antiviral agent containing a quaternary ammonium salt as an active ingredient. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6182386 [Patent Document 2] Patent No. 6137716 [Patent Document 3] Patent No. 6892031 [Patent Document 4] Patent No. 6888726 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, Patent Documents 3 and 4 disclose the addition of an antiviral agent to the surface protective layer. By adding an antiviral agent to the surface protective layer, for example, when a virus adheres to the surface protective layer, the virus is effectively inactivated.

[0007] Patent Document 4 discloses an antiviral agent containing a quaternary ammonium salt. However, antiviral agents containing a quaternary ammonium salt have low heat resistance. Therefore, for example, when a heat treatment is performed during the production of a laminate sheet, the antiviral agent may be decomposed, and discoloration due to the decomposition may occur.

[0008] The present disclosure has been made in view of the above-described circumstances, and aims to provide a laminate sheet having a surface protective layer that has both antiviral properties and heat resistance. [Means for solving the problem]

[0009] The present disclosure provides a laminate sheet for use in a building material, the laminate sheet having a base material layer and a surface protective layer, the surface protective layer containing a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B. [Effects of the Invention]

[0010] The present disclosure has an effect of providing a laminate sheet having a surface protective layer that has both antiviral properties and heat resistance. [Brief explanation of the drawings]

[0011] [Figure 1]1 is a schematic cross-sectional view illustrating a laminate sheet according to the present disclosure. [Figure 2] 1 is a schematic cross-sectional view illustrating a laminate sheet according to the present disclosure. [Figure 3] 1 is a schematic cross-sectional view illustrating a laminate sheet according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0012] Below, embodiments will be described with reference to the drawings etc. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. Furthermore, to make the explanation clearer, the drawings may show the width, thickness, and shape of each part schematically compared to the actual form, but this is merely an example and should not be interpreted as limiting.

[0013] In this specification, when describing an aspect in which another component is placed on a certain component, the term "above" or "below" refers to both a case in which another component is placed directly above or below the certain component so as to be in contact with the component, and a case in which another component is placed above or below the certain component with another component interposed therebetween, unless otherwise specified. Also, in this specification, when describing an aspect in which another component is placed on the surface of a certain component, the term "on the surface" refers to both a case in which another component is placed directly above or below the certain component so as to be in contact with the component, and a case in which another component is placed above or below the certain component with another component interposed therebetween, unless otherwise specified.

[0014] The laminate sheet according to the present disclosure will be described in detail below. Fig. 1 is a schematic cross-sectional view illustrating an example of a laminate sheet according to the present disclosure. The laminate sheet 10 shown in Fig. 1 has a base material layer 1 and a surface protective layer 2. The surface protective layer 2 contains a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B.

[0015] 2 is a schematic cross-sectional view illustrating a laminate sheet according to the present disclosure, showing a layer structure suitable for, for example, a decorative sheet for a wall (wallpaper). T 3 has, in this order, a base layer 1, a foamed resin layer 3, a decorative layer 4, a film layer 5, and a surface protective layer 2. FIG. 3 is a schematic cross-sectional view illustrating an example of a laminate sheet according to the present disclosure, showing a layer structure suitable for, for example, a decorative floor sheet. The laminate sheet 10 shown in FIG. 3 has a thickness direction D T The laminated sheet has a base layer 1, a decorative layer 4, a film layer 5, a primer layer 6 and a surface protective layer 2 in this order.

[0016] According to the present disclosure, by using antiviral agent A and antiviral agent B, a laminate sheet having a surface protective layer that combines antiviral properties and heat resistance is obtained. As mentioned above, Patent Document 4 discloses an antiviral agent containing a quaternary ammonium salt. However, antiviral agents containing a quaternary ammonium salt have low heat resistance. Therefore, for example, if a heat treatment is performed during the production of the laminate sheet, the antiviral agent may decompose, and discoloration due to the decomposition may occur. In particular, in the case of decorative wall sheets and decorative floor sheets described below, heat treatment is often performed during their production, so a surface protective layer that is less susceptible to deterioration due to the heat treatment is required.

[0017] In contrast, the present disclosure uses a cationic polymer-based antiviral agent A. Cationic polymer-based antiviral agents have cationic functional groups such as quaternary ammonium salt groups incorporated into the polymer structure, and therefore have high heat resistance. Therefore, even if a heat treatment is performed during the production of a laminate sheet, for example, decomposition of the antiviral agent can be suppressed.

[0018] Furthermore, for example, when a cationic polymer-based antiviral agent A is used and discoloration caused by decomposition of the antiviral agent A is to be sufficiently suppressed, the amount of antiviral agent A used is limited, and a surface protective layer with good antiviral properties may not be obtained. In contrast, for example, when a cationic polymer-based antiviral agent A is used and good antiviral properties are to be obtained, the amount of antiviral agent A used is large, and a surface protective layer in which discoloration caused by decomposition of the antiviral agent A is not to be sufficiently suppressed may not be obtained. Thus, when a cationic polymer-based antiviral agent A is used, although heat resistance can be improved compared to conventional antiviral agents containing quaternary ammonium salts (antiviral agents that are not polymer-based), it is difficult to obtain a laminate sheet having a surface protective layer that combines antiviral properties and heat resistance.

[0019] In the present disclosure, a silver- or silver-zinc-based antiviral agent B is used in addition to a cationic polymer-based antiviral agent A. Because antiviral agent B is an inorganic antiviral agent, it has even higher heat resistance than antiviral agent A. By using antiviral agents A and B in combination, better antiviral properties can be obtained while limiting the amount of antiviral agent A used (i.e., while suppressing discoloration due to decomposition of antiviral agent A) compared to when antiviral agent A is used alone. In this way, using antiviral agents A and B results in a laminate sheet having a surface protective layer that combines antiviral properties and heat resistance.

[0020] Furthermore, although a silver- or silver-zinc-based antiviral agent B has higher light resistance (less susceptible to discoloration due to light) than, for example, a copper- or silver-copper-based antiviral agent, its light resistance is lower than that of a cationic polymer-based antiviral agent A. For example, when antiviral agent B is used and attempts are made to sufficiently suppress discoloration due to light, the amount of antiviral agent B used is limited, and a surface protective layer with good antiviral properties may not be obtained. In contrast, when antiviral agent B is used and attempts are made to obtain good antiviral properties, the amount of antiviral agent B used is large, and a surface protective layer that sufficiently suppresses discoloration due to light may not be obtained. As such, focusing on antiviral agent B makes it difficult to obtain a laminate sheet having a surface protective layer that combines antiviral properties and light resistance. In the present disclosure, by using antiviral agent A and antiviral agent B in combination, good antiviral properties can be obtained while limiting the amount of antiviral agent B used (i.e., suppressing discoloration due to light) compared to using antiviral agent B alone. Based on these viewpoints, by using antiviral agent A and antiviral agent B in combination, it is possible to achieve both antiviral property and light resistance, and also to achieve both antiviral property and heat resistance, that is, it is possible to achieve both antiviral property, heat resistance, and light resistance.

[0021] 1.Surface protection layer The surface protective layer in the present disclosure contains a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B. As shown in FIG. 1 , the laminate sheet 10 may have a surface protective layer 2 as the outermost layer.

[0022] (1) Antiviral agent A The antiviral agent A in the present disclosure is a cationic polymer-based antiviral agent. The surface protective layer may contain only one type of antiviral agent A, or may contain two or more types. A cationic polymer refers to a polymer having a cationic functional group. Examples of the cationic functional group include a quaternary ammonium base and a quaternary phosphonium base. A cationic polymer usually has a cationic functional group in at least one of its main chain and side chain. A cationic polymer may have a cationic functional group in its main chain but not in its side chain. Alternatively, a cationic polymer may have a cationic functional group in its side chain but not in its main chain. Alternatively, a cationic polymer may have a cationic functional group in its main chain and not in its side chain.

[0023] The antiviral agent A preferably has a quaternary ammonium base as the cationic functional group, because this provides excellent antiviral properties. When the antiviral agent A has a quaternary ammonium base in the main chain, it may have a structural unit represented by the following (1):

[0024] [ka]

[0025] In the above (1), R 1 ~R 4 R is each independently a functional group containing at least carbon. 1 and R 2 The number of carbon atoms in R is, for example, 1 or more and 10 or less, and may be 1 or more and 5 or less. 1 and R 2 are, for example, alkylene groups. 1 and R 2 At least one of R may have a quaternary ammonium salt group. 3 and R 4 The number of carbon atoms in each of R is, for example, 1 or more and 10 or less, and may be 1 or more and 5 or less. 3 and R 4is, for example, a hydrocarbon group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, the hydrogen (H) of the hydrocarbon group may be substituted with another element or a functional group. It is preferable that the antiviral agent A has the structural unit represented by (1) above as the main component of the main chain. This is because the heat resistance of the antiviral agent A is improved.

[0026] The antiviral agent A may have a structural unit represented by the following (2):

[0027] [ka]

[0028] In the above (2), R 11 is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms, and four R 11 may be the same or different from each other. 12 is an alkylene group having 2 to 10 carbon atoms. 13 is a heteroalkylene group having 2 to 6 carbon atoms, or a heteroalkylene group having a hydroxyl group. - is an anion.

[0029] Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Examples of hydroxyalkyl groups having 1 to 4 carbon atoms include hydroxymethyl, hydroxyethyl, hydroxypropyl, 1-methyl-1-hydroxyethyl, and 1-methyl-2-hydroxyethyl. Examples of alkenyl groups having 2 to 4 carbon atoms include vinyl and allyl. The alkylene group having 2 to 10 carbon atoms may be a linear or branched alkylene group. Examples of alkylene groups include ethylene, propylene, trimethylene, tetramethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, and decamethylene. The heteroalkylene group having 2 to 6 carbon atoms or the heteroalkylene group having a hydroxyl group preferably has at least one of oxygen and sulfur as a heteroatom. Examples of such heteroalkylene groups include methyleneoxymethylene, methyleneoxyethylene, ethyleneoxyethylene, ethyleneoxymethyleneoxyethylene, methylenethiomethylene, methylenethioethylene, and ethylenethioethylene groups. Examples of heteroalkylene groups having a hydroxyl group include 1-hydroxy-3-oxapentylene and 1,4-dihydroxy-2-oxabutylene groups. - Examples of the anion represented by the formula (2) include anions derived from monovalent or polyvalent carboxylic acids such as formic acid, acetic acid, propionic acid, gluconic acid, lactic acid, fumaric acid, maleic acid, adipic acid, and tartaric acid, acidic phosphate ester anions, alkyl sulfate ester anions, halogen anions, phosphate anions, sulfate anions, and nitrate anions. The antiviral agent A preferably has the structural unit represented by the formula (2) above as the main component of its main chain.

[0030] When the antiviral agent A has a quaternary ammonium base in a side chain, the antiviral agent A may have a structural unit having a side chain represented by the following (3):

[0031] [ka]

[0032] In the above (3), R 31 ~R 34 R is each independently a functional group containing at least carbon. 31 The number of carbon atoms in R is, for example, 1 or more and 10 or less, and may be 1 or more and 5 or less. 31 is, for example, an alkylene group. 32 ~R 34 The number of carbon atoms in each of R is, for example, 1 or more and 10 or less, and may be 1 or more and 5 or less. 32 ~R 34 is, for example, a hydrocarbon group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, the hydrogen (H) of the hydrocarbon group may be substituted with another element or a functional group.

[0033] The antiviral agent A may be a cationic olefin resin. The cationic olefin resin has an olefin such as ethylene or propylene in its structural skeleton. The antiviral agent A may also be a cationic urethane resin or a cationic amine resin. The antiviral agent A may also have a synthetic polymer such as an olefin in its structural skeleton, or may also have a natural polymer such as chitin or chitosan in its skeletal structure. The antiviral agent A may also be water-soluble. The antiviral agent A may also be in an emulsion state.

[0034] The weight-average molecular weight (Mw) of the antiviral agent A is not particularly limited, but may be, for example, 10,000 or more, or 30,000 or more. If the weight-average molecular weight is too small, the antiviral agent A may not exhibit good heat resistance. On the other hand, the weight-average molecular weight (Mw) of the antiviral agent A may be, for example, 1,000,000 or less, or 800,000 or less. If the weight-average molecular weight is too large, the antiviral agent A may not exhibit good antiviral properties. The weight-average molecular weight in the present disclosure can be determined as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0035] Specific examples of antiviral agent A include Amorden D-CL50 (manufactured by Yamato Chemical Industry Co., Ltd.), Biocide Neo (manufactured by Taisho Technos Co., Ltd.), Nikkanon RB (manufactured by Nicca Chemical Co., Ltd.), FC-V20S (manufactured by Fuji Chemical Industry Co., Ltd.), Marukaside CP (manufactured by Osaka Kasei Co., Ltd.), and Arrowbase (manufactured by Unitika Co., Ltd.).

[0036] The content of the antiviral agent A is, for example, 0.1 parts by mass or more, or may be 0.5 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more, relative to 100 parts by mass of the resin component. If the content of the antiviral agent A is too low, good antiviral properties may not be exhibited. On the other hand, the content of the antiviral agent A may be, for example, 15 parts by mass or less, or may be 12 parts by mass or less, relative to 100 parts by mass of the resin component. If the content of the antiviral agent A is too high, the contamination resistance of the surface protective layer may be reduced.

[0037] The total content of the antiviral agent A and the antiviral agent B is, for example, 1 part by mass or more, or may be 3 parts by mass or more, or 5 parts by mass or more, or may be 7 parts by mass or more, relative to 100 parts by mass of the resin component. If the total content of the antiviral agent A and the antiviral agent B is too low, good antiviral properties may not be exhibited. On the other hand, the total content of the antiviral agent A and the antiviral agent B may be, for example, 20 parts by mass or less, or may be 15 parts by mass or less, relative to 100 parts by mass of the resin component. If the total content of the antiviral agent A and the antiviral agent B is too high, the contamination resistance of the surface protective layer may be reduced.

[0038] The mass ratio (A / B) of antiviral agent A to antiviral agent B is, for example, 0.05 or more, or may be 0.1 or more, or may be 0.5 or more. On the other hand, the mass ratio (A / B) is, for example, 10 or less, or may be 5 or less.

[0039] (2) Antiviral agent B The antiviral agent B in the present disclosure is a silver-based or silver-zinc-based antiviral agent. The surface protective layer may contain only one type of antiviral agent B, or may contain two or more types. For example, the surface protective layer may contain a silver-based antiviral agent and a silver-zinc-based antiviral agent. Furthermore, a silver-based antiviral agent is typically an antiviral agent containing only silver as the active ingredient. On the other hand, a silver-zinc-based antiviral agent is typically an antiviral agent containing at least silver and zinc as active ingredients, or may be an antiviral agent containing only silver and zinc as active ingredients. The antiviral agent B typically contains a carrier and metal ions (silver ions, zinc ions) supported on or contained in the carrier.

[0040] The carrier in antiviral agent B may be an inorganic material or an organic material. Examples of inorganic materials include glass, apatite, zeolite, zirconium phosphate, and titanium phosphate. In particular, when glass or apatite is used, discoloration can be suppressed. Examples of glass include soda glass, borosilicate glass, lead glass, aluminosilicate glass, borate glass, and phosphate glass.

[0041] Apatite is a general term for minerals having a composition represented by the following general formula: M 10 (ZO4)3X2 In the above formula, M is at least one of Ca, Ba, Mg, Na, K, Fe, and Al, Z is at least one of P, S, Si, and As, and X is at least one of F, Cl, O, and OH. Specific examples of apatite include fluorapatite (Ca 10 (PO4)6F2), hydroxyapatite (Ca 10 (PO4)6(OH)2).

[0042] Examples of organic materials include resins, such as copolymers of styrenes or α-olefins with (meth)acrylic acid, and polyacetal resins.

[0043] Antiviral agent B usually comprises a carrier and an active ingredient (metal ion) supported on or contained in the carrier. Here, "the active ingredient is contained in the carrier" means that the active ingredient or a substance capable of generating the active ingredient is held in the carrier. Furthermore, "a substance capable of generating an active ingredient" means a substance that generates the active ingredient due to an external factor or a factor over time, such as a substance that generates the active ingredient by dissolving in water. Examples of substances capable of generating an active ingredient include simple metals, metal alloys, inorganic salts, oxides, and hydroxides.

[0044] The active ingredient or a substance capable of generating the active ingredient (hereinafter referred to as the active ingredient, etc.) may be supported on or contained in a carrier by physical or chemical adsorption. The active ingredient may also be supported on or contained in a carrier by an ion exchange reaction. The substance capable of generating the active ingredient may also be supported on or contained in a carrier by a binder.

[0045] The amount of the active ingredient in antiviral agent B is, for example, 0.1 parts by mass or more and 30 parts by mass or less, or alternatively 0.5 parts by mass or more and 25 parts by mass or less, or 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the carrier.

[0046] The antiviral agent B is preferably, for example, in the form of particles. Examples of the particle shape of the antiviral agent B include spheres, ellipsoids, polyhedrons, and scales. The average particle diameter of the antiviral agent B is, for example, 0.5 μm or more and 10 μm or less, and may be 1.0 μm or more and 5.0 μm or less. The average particle diameter in the present disclosure is the cumulative 50% value (D 50 , median diameter).

[0047] The average particle size of antiviral agent B is D B and the thickness of the surface protection layer is T. B / T may be less than or equal to 1 or may be greater than 1. B When / T is 1 or less, the antiviral agent B can be prevented from protruding from the surface of the surface protective layer. B / T may be 0.8 or less, or may be 0.6 or less. B / T is, for example, 0.1 or more.

[0048] Specific examples of the antiviral agent B include Novalon IV-1000 (manufactured by Toagosei), Amteclean Z (manufactured by Amtec), and Zeomic (manufactured by Sinanen Zeomic).

[0049] The content of the antiviral agent B is, for example, 0.1 parts by mass or more, or may be 0.5 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more, relative to 100 parts by mass of the resin component. If the content of the antiviral agent B is too low, good antiviral properties may not be exhibited. On the other hand, the content of the antiviral agent B may be, for example, 15 parts by mass or less, or may be 12 parts by mass or less, relative to 100 parts by mass of the resin component. If the content of the antiviral agent B is too high, the contamination resistance of the surface protective layer may be reduced.

[0050] (3) Resin component The surface protective layer contains a resin component. The resin component mainly functions as a binder resin. The surface protective layer preferably contains, as the resin component, at least one of a resin composition and a cured product thereof. The cured product may be a cured product obtained by curing a curable resin composition with ionizing radiation, or a cured product obtained by curing a curable resin composition with heat.

[0051] Examples of the curable resin composition include an ionizing radiation-curable resin composition and a thermosetting resin composition. From the viewpoints of scratch resistance and production efficiency, an ionizing radiation-curable resin composition is preferred. That is, the surface protective layer preferably contains a cured product of an ionizing radiation-curable resin composition as a resin component.

[0052] Specific examples of the ionizing radiation curable resin composition include an electron beam curable resin composition and an ultraviolet ray curable resin composition. electron beam The curable resin composition has advantages such as less odor and less discoloration because it does not require a polymerization initiator.

[0053] The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as "ionizing radiation-curable compound"). The ionizing radiation-curable functional group is a group that undergoes crosslinking and curing upon irradiation with ionizing radiation. Specific examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. Other specific examples of the ionizing radiation-curable functional group include an epoxy group and an oxetanyl group. In this specification, a (meth)acryloyl group refers to an acryloyl group or a methcroyl group. In this specification, a (meth)acrylate refers to an acrylate or a methacrylate. Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Specific examples of ionizing radiation include ultraviolet (UV) rays and electron beams (EB). Other specific examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0054] The ionizing radiation-curable resin composition may contain only one type of ionizing radiation-curable compound, or may contain two or more types. The type of ionizing radiation-curable compound is not particularly limited, and known polymerizable monomers and known polymerizable oligomers (polymerizable prepolymers) can be used.

[0055] The ionizing radiation-curable compound preferably contains a compound having two or more ethylenically unsaturated bond groups. In particular, the ionizing radiation-curable compound preferably contains a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. The polyfunctional (meth)acrylate compound may be a monomer or an oligomer.

[0056] The polyfunctional (meth)acrylate compound may be a bifunctional (meth)acrylate monomer or a trifunctional or higher functional (meth)acrylate monomer. Examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate. Examples of trifunctional or higher functional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate.

[0057] Examples of polyfunctional (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

[0058] Urethane (meth)acrylates can be obtained, for example, by reacting polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates. Epoxy (meth)acrylates can be obtained, for example, by reacting epoxy resins with (meth)acrylic acid. At least one of polybasic acids and phenols may be further used in this reaction. Epoxy resins may be bifunctional, trifunctional, or higher. Examples of epoxy resins include aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

[0059] The ionizing radiation curable compound may contain silicone (meth)acrylate. The use of silicone (meth)acrylate improves the contamination resistance of the surface protective layer. Examples of silicone (meth)acrylate include silicone oil containing polysiloxane. The silicone (meth)acrylate may be a modified silicone oil in which a (meth)acrylic group is introduced at the end of polysiloxane. The content of silicone (meth)acrylate is, for example, 1 part by mass or more and 7 parts by mass or less, or may be 2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the ionizing radiation curable compound (excluding silicone (meth)acrylate).

[0060] When the ionizing radiation-curable compound is an ultraviolet-curable compound, the ionizing radiation-curable resin composition preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of photopolymerization initiators include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, and thioxanthone. Examples of photopolymerization accelerators include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0061] On the other hand, a thermosetting resin composition is a composition containing at least a thermosetting resin. This resin composition is cured by heating. Examples of thermosetting resins include acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. The thermosetting resin composition may contain additives such as a curing agent and a curing catalyst, as needed.

[0062] (4) Additives The surface protective layer may further contain at least one additive selected from the group consisting of an antioxidant, a light stabilizer, and an ultraviolet absorber. Examples of antioxidants include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Among these, phosphorus-based antioxidants can effectively suppress discoloration of the surface protective layer due to light. Examples of light stabilizers include hindered amine compounds. Hindered amine compounds typically have a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule. Examples of hindered amine compounds include NH-type hindered amine compounds, NR-type hindered amine compounds, and NOR-type hindered amine compounds. Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.

[0063] (5) Surface protective layer The surface protection layer according to the present disclosure contains at least a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B. The thickness of the surface protection layer is not particularly limited, but is, for example, 1.0 μm or more and 20 μm or less, or alternatively 1.5 μm or more and 15 μm or less, or 2.0 μm or more and 10 μm or less.

[0064] Examples of methods for forming the surface protective layer include a method in which a mixture containing a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B is applied to the surface of a base layer, dried, and cured. Alternatively, the mixture may be applied to the surface of a substrate having releasability, dried, and cured to form a surface protective layer, which may then be transferred onto the base layer.

[0065] 2.Base material layer The substrate layer in the present disclosure is a layer that supports the surface protective layer. Examples of materials constituting the substrate layer include fibrous materials, resins, metals, and non-metallic inorganic materials. The substrate layer may be a single layer or a laminate of two or more layers. In the latter case, the substrate layer may have two or more layers made of the same type of constituent material, or two or more layers made of different types of constituent material.

[0066] Examples of fibrous materials used in the substrate layer include tissue paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, wallpaper backing paper, paperboard, and plasterboard base paper. The paper may be either ordinary paper or flame-retardant paper. Flame-retardant paper is ordinary paper containing a flame retardant. Examples of flame retardants include nitrogen compounds such as urea and ammonium compounds, hydroxides (preferably hydrates) such as magnesium hydroxide and aluminum hydroxide, and self-extinguishing flame retardants containing phosphorus or halogen elements. Among these, compounds containing water of crystallization, such as magnesium hydroxide, can be flame-retarded by the heat of vaporization of the water of crystallization during combustion and decomposition.

[0067] Other examples of fibrous materials include woven fabrics and nonwoven fabrics. Examples of fibers used in woven fabrics or nonwoven fabrics include resin fibers (e.g., polyester resin fibers, acrylic resin fibers), natural fibers (e.g., silk, cotton, and linen), glass fibers, and carbon fibers. When a fibrous material is used for the substrate layer, a resin such as an acrylic resin, styrene-butadiene rubber, melamine resin, or urethane resin may be added (by impregnation with the resin after papermaking or by filling the resin during papermaking). The substrate layer may also be a wallpaper roll in which a resin layer such as a vinyl chloride resin layer, an olefin resin layer, or an acrylic resin layer is laminated on the surface of wallpaper backing paper.

[0068] Examples of resins used in the base layer include synthetic resins and natural resins. Examples of synthetic resins include thermoplastic resins. Examples of thermoplastic resins include olefin-based resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and olefin-based thermoplastic elastomers; vinyl chloride-based resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide-based resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane, and celluloid; and styrene-based resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene copolymers (ABD). Other examples of thermoplastic resins include polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, and polyimide resin. Examples of natural resins include natural rubber, pine resin, and amber.

[0069] Examples of metals used for the substrate layer include aluminum, aluminum alloys (e.g., duralumin), iron, iron alloys (e.g., carbon steel, stainless steel), copper, copper alloys (e.g., brass, bronze), gold, silver, chromium, nickel, cobalt, tin, and titanium. The surface of the metal may be plated.

[0070] Examples of non-metallic inorganic materials used in the base layer include non-ceramic ceramic materials such as cement, ALC (aerated lightweight concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as porcelain, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, and andesite.

[0071] The substrate layer may contain additives such as flame retardants, inorganic agents, dry strength agents, wet strength agents, colorants, sizing agents, and fixing agents, as needed. The substrate layer may also be subjected to a surface treatment, for example, to improve adhesion. Examples of surface treatments include oxidation and roughening. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment. Examples of roughening methods include sandblasting and solvent treatment.

[0072] The substrate layer may be in the form of a sheet, for example. The thickness of the substrate layer is not particularly limited, but is, for example, 10 μm or more and 300 μm or less. The basis weight of the substrate layer is not particularly limited, but is, for example, 50 g / m 2 More than 300g / m 2 less than 60 g / m 2 More than 160g / m 2 It may be the following:

[0073] 3.Laminated sheet The laminate sheet of the present disclosure has at least a substrate layer and a surface protective layer. The laminate sheet may have only the substrate layer and the surface protective layer, or may have other layers in addition to the substrate layer and the surface protective layer. Examples of the other layers include a foamed resin layer, a non-foamed resin layer, a decorative layer, a primer layer, a film layer, and an adhesive layer.

[0074] Examples of the layer structure of the laminated sheet include the layer structures shown below. (1) Base layer / foamed resin layer / surface protection layer (2) Base layer / foamed resin layer / primer layer / surface protection layer (3) Base layer / foamed resin layer / decorative layer / surface protection layer (4) Base layer / foamed resin layer / decorative layer / primer layer / surface protection layer (5) Base layer / foamed resin layer / adhesive layer / film layer / surface protection layer (6) Base material layer / foamed resin layer / adhesive layer / decorative layer / film layer / surface protection layer (7) Base material layer / foamed resin layer / decorative layer / adhesive layer / film layer / surface protection layer (8) Base layer / foamed resin layer / film layer / primer layer / surface protection layer (9) Base layer / foamed resin layer / adhesive layer / film layer / primer layer / surface protection layer (10) Base layer / Foamed resin layer / Adhesive layer / Decorative layer / Film layer / Primer layer / Surface protection layer (11) Base material layer / foamed resin layer / decorative layer / adhesive layer / film layer / primer layer / surface protection layer (12) Base material layer / surface protection layer (13) Base layer / primer layer / surface protection layer (14) Base layer / decorative layer / surface protection layer (15) Base layer / decorative layer / primer layer / surface protection layer (16) Base layer / adhesive layer / film layer / surface protection layer (17) Base layer / adhesive layer / decorative layer / film layer / surface protection layer (18) Base layer / decorative layer / adhesive layer / film layer / surface protection layer (19) Base layer / Film layer / Primer layer / Surface protection layer (20) Base layer / adhesive layer / film layer / primer layer / surface protection layer (21) Base layer / adhesive layer / decorative layer / film layer / primer layer / surface protection layer (22) Base layer / decorative layer / adhesive layer / film layer / primer layer / surface protection layer

[0075] The " / " indicates the relative positional relationship of each layer; for example, "A / B / C" means that A, B, and C are arranged in that order along the thickness direction. Furthermore, for example, when written as "A / B," A and B may be arranged so as to be in direct contact with each other, or may be arranged via another layer. Furthermore, as exemplified in (1) to (11) above, when the laminate sheet has a foamed resin layer, a non-foamed resin layer may be arranged on one or both sides of the foamed resin layer.

[0076] (1) Foamed resin layer The laminate sheet may have a foamed resin layer between the base layer and the surface protective layer. Providing a foamed resin layer improves the design and texture of the laminate sheet. In particular, when the laminate sheet is used as a decorative wall sheet (wallpaper), it is preferable that the laminate sheet has a foamed resin layer. On the other hand, the laminate sheet may not have a foamed resin layer. Furthermore, the laminate sheet in the present disclosure may be a sheet before the foamed resin layer is formed. In this case, the laminate sheet has a foaming agent-containing resin layer, which will be described later.

[0077] The foamed resin layer contains a resin. The foamed resin layer may contain a cured product of the resin. Examples of the resin include thermoplastic resins. Examples of the thermoplastic resin include polyvinyl chloride resins, olefin resins, polystyrene resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers, nylon, polyacetal resins, acrylic resins, polycarbonate resins, polyester resins, polyvinyl acetate resins, polyvinyl alcohol resins, and polyurethane resins.

[0078] The foamed resin layer preferably contains an olefin-based resin as the resin, such as polyolefin, olefin vinyl ester copolymer, olefin-unsaturated carboxylic acid copolymer, or olefin-unsaturated carboxylic acid ester copolymer.

[0079] Examples of polyolefins include polyethylene (PE) and polypropylene (PP), with PE being preferred. Examples of PE include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and linear low-density polyethylene (LLDPE).

[0080] The olefin-vinyl ester copolymer is a copolymer containing an olefin and a vinyl ester as monomer components, and may be a binary or ternary copolymer. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Examples of the vinyl ester include vinyl acetate, vinyl caproate, vinyl propionate, vinyl caprylate, vinyl laurate, and vinyl stearate.

[0081] Specific examples of olefin vinyl ester copolymers include ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl caproate copolymer, ethylene-vinyl propionate copolymer, ethylene-vinyl caprylate copolymer, ethylene-vinyl laurate copolymer, and ethylene-vinyl stearate copolymer.

[0082] The olefin-unsaturated carboxylic acid copolymer is a copolymer containing an olefin and an unsaturated carboxylic acid as monomer components, and may be a binary or ternary copolymer. Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, and fumaric acid.

[0083] Specific examples of the olefin-unsaturated carboxylic acid copolymer include ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA).

[0084] Examples of the olefin unsaturated carboxylic acid ester copolymer include ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-ethyl methacrylate copolymer (EEMA).

[0085] The foamed resin layer may contain an inorganic filler. The addition of an inorganic filler improves flame retardancy. Examples of inorganic fillers include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, molybdenum compounds, and titanium dioxide. The content of the inorganic filler is, for example, 30 parts by mass or more and 150 parts by mass or less, or may be 40 parts by mass or more and 100 parts by mass or less, relative to 100 parts by mass of the resin constituting the foamed resin layer. The average particle diameter (D 50 ) is, for example, 5 μm or more and 25 μm or less, and may be 5 μm or more and 15 μm or less.

[0086] The foamed resin layer has bubbles therein. The bubbles may be closed or open. The foamed resin layer may contain both closed and open cells. The bubbles are formed by foaming of the foaming agent contained in the foaming-agent-containing resin layer, and the number, size, density, and shape of the bubbles are not particularly limited.

[0087] The foamed resin layer may contain additives such as pigments, antioxidants, light stabilizers, crosslinking agents, crosslinking aids, foaming aids, insect repellents, preservatives, antibacterial agents, diluents, deodorizers, and plasticizers, as needed. The foamed resin layer may also contain an unfoamed foaming agent. The thickness of the foamed resin layer is, for example, 350 μm or more and 1500 μm or less, or may be 500 μm or more and 1200 μm or less.

[0088] The method for forming the foamed resin layer is not particularly limited, but includes a method of heating and foaming a foaming-agent-containing resin layer containing a resin and a foaming agent to form a foamed resin layer. Examples of the foaming agent include organic thermal decomposition-type foaming agents. Examples of the organic thermal decomposition-type foaming agents include azo-based foaming agents such as azodicarbonamide (ADCA) and azobisformamide, and hydrazide-based foaming agents such as oxybenzenesulfonylhydrazide (OBSH) and paratoluenesulfonylhydrazide. Other specific examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate. The foaming agent may also be a microcapsule-type foaming agent. Examples of the method for forming the foaming-agent-containing resin layer include extrusion film formation using an extruder such as a T-die extruder.

[0089] (2) Non-foamed resin layer The laminate sheet may have a non-foamed resin layer between the base layer and the surface protective layer. The non-foamed resin layer is a layer that does not contain bubbles caused by foaming of a foaming agent. When the laminate sheet has a foamed resin layer, the non-foamed resin layer may be disposed on the surface of the foamed resin layer facing the base layer, or on the surface of the foamed resin layer facing the surface protective layer. On the other hand, the laminate sheet does not have to have a non-foamed resin layer.

[0090] Here, the non-foamed resin layer disposed on the surface of the foamed resin layer facing the substrate layer is referred to as the non-foamed resin layer A. By providing the non-foamed resin layer A, the adhesion between the foamed resin layer and the substrate layer is improved. The non-foamed resin layer A contains a resin and may contain a cured product of the resin. Details of the non-foamed resin layer A are the same as those described above in "(1) Foamed Resin Layer" except for the use of a foaming agent, so they will not be described here. The non-foamed resin layer A and the foamed resin layer may contain the same type of resin or different types of resin. The thickness of the non-foamed resin layer A is, for example, 5 μm or more and 50 μm or less.

[0091] The non-foamed resin layer disposed on the surface of the foamed resin layer facing the surface protective layer is referred to as the non-foamed resin layer B. The provision of the non-foamed resin layer B can, for example, improve the design of the decorative layer or the scratch resistance of the foamed resin layer. The non-foamed resin layer B contains a resin and may contain a cured product of the resin. Details of the non-foamed resin layer B are the same as those described above in "(1) Foamed Resin Layer" except for the use of a foaming agent, and therefore will not be described here. The non-foamed resin layer B and the foamed resin layer may contain the same type of resin or different types of resin. The thickness of the non-foamed resin layer B is, for example, 5 μm or more and 10 μm or less. The laminate sheet may have both the non-foamed resin layer A and the non-foamed resin layer B.

[0092] The non-foamed resin layer may be formed, for example, by extrusion film formation using an extruder such as a T-die extruder.

[0093] (3) Decorative layer The laminate sheet may have a decorative layer between the base layer and the surface protective layer. By providing a decorative layer, the design of the laminate sheet is improved. On the other hand, the laminate sheet does not have to have a decorative layer. When the laminate sheet has a foamed resin layer, the decorative layer is preferably arranged between the foamed resin layer and the surface protective layer. When the laminate sheet has a non-foamed resin layer, the decorative layer is preferably arranged between the non-foamed resin layer and the surface protective layer. Furthermore, the laminate sheet may have a decorative layer on the surface of the surface protective layer opposite to the base layer. Furthermore, when the laminate sheet is viewed in plan in the thickness direction, the decorative layer may be arranged on the entire surface of the laminate sheet, or may be arranged on a part of the laminate sheet.

[0094] Examples of decorative layers include solid layers (layers coated with ink) and pattern layers (layers printed with ink). Examples of patterns in the pattern layer include wood grain, stone grain, sand grain, tiled patterns, brickwork patterns, fabric patterns, leather-striped patterns, geometric shapes, letters, symbols, abstract patterns, and floral patterns.

[0095] The decorative layer usually contains a colorant and a binder resin. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black; metal pigments such as aluminum and brass; and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0096] Examples of binder resins include urethane-based resins, acrylic polyol-based resins, acrylic-based resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins.

[0097] The decorative layer may contain additives such as ultraviolet absorbers, light stabilizers, curing agents, plasticizers, and catalysts as needed. The thickness of the decorative layer is, for example, 0.5 μm to 20 μm, or 1 μm to 10 μm, or 2 μm to 5 μm. The decorative layer may be formed, for example, by applying an ink containing a colorant, a binder resin, and a solvent, followed by drying.

[0098] (4) Primer layer The laminate sheet may have a primer layer on the surface of the surface protective layer facing the substrate layer. By providing the primer layer, the adhesion between the substrate layer and the surface protective layer is improved, and for example, a decrease in interlayer adhesion upon exposure to ultraviolet light can be suppressed. Furthermore, by providing the primer layer, the scratch resistance of the surface protective layer is improved. Furthermore, the laminate sheet may have a primer layer (rear primer layer) on the surface of the substrate layer opposite the surface protective layer.

[0099] The primer layer contains at least a binder resin. Examples of binder resins include urethane-based resins, acrylic polyol-based resins, acrylic-based resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins. The primer layer may contain only one type of resin, or two or more types.

[0100] The primer layer may contain a cured binder resin. Examples of the curing agent include an isocyanate curing agent and an epoxy curing agent. The cured binder resin is preferably a cured product obtained by crosslinking and curing a polyol resin such as an acrylic polyol resin with an isocyanate curing agent.

[0101] The primer layer may further contain at least one of an ultraviolet absorber and a light stabilizer. Conventional ultraviolet absorbers and light stabilizers can be used. The thickness of the primer layer is, for example, 0.01 μm or more and 10 μm or less, or 0.7 μm or more and 8 μm or less, or 1 μm or more and 6 μm or less. The primer layer may be formed, for example, by applying a resin composition containing a binder resin and a solvent, followed by drying. A curing treatment may be performed as necessary.

[0102] (5) Film layer The laminate sheet may have a film layer between the substrate layer and the surface protective layer. The provision of the film layer improves the strength of the laminate sheet. In particular, when the laminate sheet is used as a decorative floor sheet, it is preferable that the laminate sheet have a film layer. This is because high strength is required for decorative floor sheets. When the laminate sheet has a primer layer, it is preferable that the film layer be disposed between the substrate layer and the primer layer. Furthermore, when the laminate sheet has a decorative layer, it is preferable that the film layer be disposed between the decorative layer and the surface protective layer. This is because the film layer can effectively protect the decorative layer.

[0103] The film layer may be transparent, translucent, or opaque. The film layer may be colored or uncolored. When the laminate sheet has a decorative layer, the film layer preferably has transparency that allows the decorative layer to be identified.

[0104] The film layer contains a resin. Examples of the resin include an olefin resin, a methacrylic resin, a polyvinyl alcohol resin, and a fluorine-based resin. The resin may be an acid-modified resin. Examples of the olefin resin include a polyolefin and an olefin copolymer. Examples of the polyolefin include polyethylene, polypropylene, polybutene, polybutadiene, and polyisoprene, with polyethylene being preferred.

[0105] The olefin copolymer is not particularly limited, but an ethylene copolymer containing ethylene is preferred. Examples of the ethylene copolymer include ethylene-α,β-unsaturated carboxylic acid ester copolymers. Examples of the ethylene-α,β-unsaturated carboxylic acid ester copolymers include ethylene-methacrylic acid copolymers (EMAA).

[0106] The thickness of the film layer is, for example, 3 μm or more and 25 μm or less, and may be 5 μm or more and 20 μm or less. Examples of methods for forming the film layer include extrusion film formation using an extruder such as a T-die extruder. Alternatively, the film layer may be prepared in advance and then thermally laminated with other layers. If necessary, a curing treatment may be performed.

[0107] (6) Adhesive layer The laminate sheet may have an adhesive layer. The position of the adhesive layer is not particularly limited. When the laminate sheet has a foamed resin layer, the adhesive layer may be disposed on the surface of the foamed resin layer opposite the substrate layer. When the laminate sheet has a non-foamed resin layer B, the adhesive layer may be disposed on the surface of the non-foamed resin layer B opposite the substrate layer. When the laminate sheet has a film layer, the adhesive layer may be disposed between the substrate layer and the film layer. When the laminate sheet has a decorative layer, the adhesive layer may be disposed on the surface of the decorative layer opposite the substrate layer. When the substrate layer is a laminate of two or more layers, an adhesive layer may be disposed between each layer constituting the substrate layer. The laminate sheet may also have an adhesive layer on the surface of the substrate layer opposite the surface protective layer. In this case, the laminate sheet may have a peelable separator layer on the surface of the adhesive layer opposite the substrate layer.

[0108] The adhesive layer contains a resin, such as ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA), ethylene-(meth)acrylic acid copolymer (EMAA), acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine-containing resins, silicone resins, cellulose derivatives, and rubber resins.

[0109] The thickness of the adhesive layer is, for example, 0.1 μm or more and 10 μm or less. The adhesive layer can be formed, for example, by applying a resin composition containing a resin and a solvent, followed by drying.

[0110] (7) Laminated sheet The laminate sheet according to the present disclosure includes at least a substrate layer and a surface protective layer, and may further include other layers, such as a foamed resin layer, a non-foamed resin layer, a decorative layer, a primer layer, a film layer, or an adhesive layer, as described above.

[0111] The laminate sheet may have an embossed pattern on the outermost surface of the surface protective layer side relative to the base layer. It is particularly preferable that the embossed pattern be disposed on the surface of the surface protective layer opposite the base layer. Because the surface protective layer of the present disclosure has good heat resistance, even when subjected to heat treatment to form an embossed pattern, the laminate sheet has good antiviral properties. Examples of embossed patterns include wood grain vascular grooves, stone slab surface irregularities, cloth surface texture, matte finish, sand grain, hairline, and linear grooves.

[0112] The embossed pattern can be formed, for example, by heating the laminated sheet and pressing an embossing plate against it. The heating temperature of the laminated sheet is, for example, 80°C or higher and 260°C or lower, or alternatively, 85°C or higher and 200°C or lower, or 100°C or higher and 180°C or lower.

[0113] The laminate sheet in the present disclosure is typically a decorative sheet, and is generally used as a building material. Specific examples include the following (1) to (5).

[0114] (1) Surface materials for interior walls, floors, ceilings, etc. of buildings such as houses, offices, stores, hospitals, and clinics (2) Surface materials for exterior walls, roofs, eaves, door pockets, etc. of buildings such as houses, offices, stores, hospitals, and clinics (3) Surface materials for windows, window frames, doors, door frames, and other fixtures (4) Surface materials for fixtures such as handrails, waist walls, moldings, thresholds, lintels, and top boards (5) Surface materials for outdoor (exterior) parts such as fences, gates, drying rack posts, and handrails

[0115] The laminate sheet in the present disclosure may be a transfer sheet. For example, when the laminate sheet has the above-described decorative layer, the laminate sheet may be a transfer sheet for transferring the decorative layer. Furthermore, the laminate sheet may be a transfer sheet for transferring the surface protective layer. Furthermore, as described above, the laminate sheet may have an adhesive layer as appropriate depending on its application.

[0116] The present disclosure also provides a method for producing a laminate sheet having a base layer and a surface protective layer, the method including a precursor sheet production step of forming a precursor sheet on one surface of the base layer, the precursor sheet containing a resin component, a cationic polymer-based antiviral agent A, and a silver-based or silver-zinc-based antiviral agent B, and a heat treatment step of heat-treating the precursor sheet. The heat treatment step can be any step of heat-treating a precursor sheet of a laminate sheet. For example, the heat treatment step is a step of foaming a foaming-agent-containing resin layer. Another example of the heat treatment step is a step of forming an embossed pattern.

[0117] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included within the technical scope of the present disclosure. [Example]

[0118] [Example 1] (Preparation of resin composition containing a foaming agent) The following materials were melt-kneaded to obtain a resin composition containing a foaming agent. Resin: EMAA "N1560: Mitsui DuPont Polychemicals Co., Ltd."...100 parts by weight Inorganic filler: Titanium dioxide "CR58-2: Ishihara Sangyo Kaisha Ltd."...20 parts by weight Foaming agent: Azo foaming agent "Vinihole AC#3: manufactured by Eiwa Chemical Industry Co., Ltd."... 4 parts by weight Foaming aid: Hydrazide-based foaming aid "ADH: manufactured by Otsuka Chemical Co., Ltd."... 2 parts by weight

[0119] (Preparation of EB coating agent) The following materials were mixed to obtain an EB coating agent. Electron beam curing resin coating agent "Seika Beam: manufactured by Dainichi Seika Chemicals Co., Ltd."...100 parts by weight Antiviral agent A: Cationic polymer antiviral agent "Amorden D-CL50" (Yamato Chemical Industry Co., Ltd.)... 1 part by mass Antiviral agent B: Silver-based antiviral agent "Novalon IV-1000: manufactured by Toagosei Co., Ltd."... 9 parts by weight

[0120] (Preparation of laminated sheets) A resin composition containing a foaming agent was formed into a film having a thickness of 50 μm or more and 100 μm or less, to obtain a foaming agent-containing resin layer. One side of the obtained foaming agent-containing resin layer was laminated to a backing paper (substrate layer). Next, an EB coating agent was applied to the other side of the foaming agent-containing resin layer using a gravure printing machine. Thereafter, electron beam irradiation was performed under conditions of 200 kV and 50 kGy to form a surface protective layer. Next, the foaming agent-containing resin layer was expanded by heating at 220°C for 40 seconds in a gear oven, to obtain a laminate sheet (foamed laminate sheet).

[0121] [Example 2] A laminated sheet was obtained in the same manner as in Example 1, except that the amount of antiviral agent A used was changed to 2.5 parts by mass.

[0122] [Example 3] A laminated sheet was obtained in the same manner as in Example 1, except that the resin in the resin composition containing a foaming agent was changed to EVA "P1007 (VA content 10%): manufactured by DuPont-Mitsui Polychemicals Co., Ltd."

[0123] [Example 4] A laminated sheet was obtained in the same manner as in Example 1, except that the antiviral agent A was changed to "FC-V20S: manufactured by Fuji Chemical Industry Co., Ltd." [Example 5] A laminated sheet was obtained in the same manner as in Example 1, except that antiviral agent B was changed to a silver-zinc antiviral agent "Amtech Clean Z: Amtech Co., Ltd."

[0124] [Comparative Example 1] A laminated sheet was obtained in the same manner as in Example 1, except that antiviral agent A and antiviral agent B were not used.

[0125] Comparative Example 2 A laminated sheet was obtained in the same manner as in Example 1, except that the antiviral agent A was changed to a quaternary ammonium salt-based antiviral agent "Suramoni D100: manufactured by Osaka Gas Chemicals Co., Ltd." and the amount of antiviral agent A used was changed to 3 parts by mass.

[0126] Comparative Example 3 A laminated sheet was obtained in the same manner as in Example 1, except that antiviral agent B was changed to a silver-copper antiviral agent "Zeomic AC10N: manufactured by Sinanen Zeomic Co., Ltd."

[0127] Comparative Example 4 A laminated sheet was obtained in the same manner as in Example 1, except that antiviral agent A was not used and the amount of antiviral agent B used was changed to 18 parts by mass.

[0128] [evaluation] (antiviral) The antiviral properties of the laminated sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated. Specifically, the tests were conducted in accordance with ISO 21702 (Determination of antiviral activity of plastics and other non-porous surfaces). The details of the tests are as follows.

[0129] 0.4 ml of virus solution was dropped onto a 5 cm square test piece (antiviral treated product and untreated product) and covered with a 4 cm square film. The test piece was left to stand at 25°C for 24 hours. After standing, the virus on the test piece was washed off and recovered, and the virus infectivity was measured. The antiviral activity value was calculated using the following formula. R=Ut-At R is the antiviral activity value, and Ut is the viral infectivity value (PFU / cm) of the unprocessed product after standing for 24 hours. 2 ) and At is the average of the common logarithm of the viral infectivity (PFU / cm) of the antiviral processed product after leaving it for 24 hours. 2 The influenza virus was used as the test virus, and an antiviral activity value of 2.0 or higher was evaluated as ◯, and an antiviral activity value of less than 2.0 was evaluated as ×.

[0130] (Stain resistance) The stain resistance of the laminated sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was evaluated. Specifically, the test was carried out in accordance with the "Stain-Resistant Wallpaper Performance Standards" established by the Wallpaper Industry Association. The details of the test are as follows.

[0131] Contaminants (coffee, soy sauce, crayon, water-based pen, and oil-based pen) were attached to the surface protective layer of the laminate sheet, and after 24 hours, the coffee and soy sauce were wiped off with water, the crayon and water-based pen with a neutral detergent, and the oil-based pen with a dry wipe. The surface protective layer after wiping was visually inspected. The surface protective layer after wiping was compared with a surface protective layer without contaminants, and grades 4 (contamination on the stain-only gray scale of about 4) and 5 (contamination on the stain-only gray scale of about 5) were evaluated as good, and grades 3 (contamination on the stain-only gray scale of about 3) or lower were evaluated as bad.

[0132] (heat resistance) The heat resistance of the laminated sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was evaluated. A spectrophotometer (CM-3700A, manufactured by Konica Minolta Inc.) was used as the measuring device. * Value(b *1 ) and b of the laminated sheets obtained in Examples 1 to 5 and Comparative Examples 2 to 4 * Value(b *2 ) and Δb * Δb * When it was less than 0.5, it was evaluated as ◯, when it was 0.5 or more but less than 1.0, it was evaluated as Δ, and when it was 1 or more, it was evaluated as x.

[0133] (Lightfastness) The light resistance of the laminate sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was evaluated. Specifically, the laminate sheets were subjected to an accelerated test using an ultraviolet autofade meter, and changes in appearance were evaluated. The details of the test are as follows.

[0134] First, a spectrophotometer (CM-3700A, manufactured by Konica Minolta) was used as a measuring device. Next, an ultraviolet autofade meter (manufactured by Suga Test Instruments Co., Ltd.) was used to measure the color of the laminated sheet at an illuminance of 500 W / m 2 The accelerated test was carried out under the conditions of a black panel temperature of 63°C for 100 hours. * Δb * When it was less than 0.5, it was evaluated as ◯, when it was 0.5 or more but less than 1.0, it was evaluated as △, and when it was 1 or more, it was evaluated as ×.

[0135] [Table 1]

[0136] As shown in Table 1, Examples 1 to 5 were all good in antiviral property, stain resistance, heat resistance, and light resistance. In contrast, Comparative Example 1 did not use an antiviral agent, and therefore did not obtain good results in the antiviral property evaluation. Comparative Example 2 did not obtain good results in the heat resistance evaluation. This is thought to be because the quaternary ammonium salt-based antiviral agent has low heat resistance. Comparative Example 3 did not obtain good results in the heat resistance and light resistance evaluation. This is thought to be because the silver-copper-based antiviral agent has low light resistance. Comparative Example 4 did not obtain good results in the stain resistance and light resistance evaluation. This is thought to be because the proportion of antiviral B was too high. [Explanation of symbols]

[0137] 1 … Base material layer 2 … Surface protective layer 3... Foam resin layer 4...Decorative layer 5...Film layer 6... Primer layer 10...Laminated sheet

Claims

1. A laminated sheet used in building materials, The laminate sheet has a base layer and a surface protective layer, The surface protective layer is A resin component, a cationic polymer antiviral agent A; a silver-based or silver-zinc-based antiviral agent B; Contains the antiviral agent A is an antiviral agent having a quaternary ammonium base in at least one of a main chain and a side chain, The surface protective layer of the laminate sheet contains, as the resin component, a cured product of an electron beam curable resin composition.

2. A laminated sheet as described in Claim 1, wherein the antiviral agent B is a silver-based antiviral agent.

3. A laminated sheet as described in claim 1, wherein the antiviral agent B is a silver-zinc based antiviral agent.

4. 3. The laminate sheet according to claim 1, wherein a content of the antiviral agent A in the surface protective layer is 0.5 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the resin component.

5. 4. The laminate sheet according to claim 1, wherein a content of the antiviral agent B in the surface protective layer is 0.5 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the resin component.

6. 6. The laminate sheet according to claim 1, wherein in the surface protective layer, a total content of the antiviral agent A and the antiviral agent B is 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the resin component.

7. The laminate sheet according to any one of claims 1 to 6, wherein the laminate sheet has the surface protection layer on the outermost surface.

8. The laminate sheet according to claim 1 , further comprising a foamed resin layer between the base material layer and the surface protective layer.

9. The laminate sheet according to claim 8, wherein the laminate sheet has a non-foamed resin layer A on the surface of the foamed resin layer facing the base material layer, and a non-foamed resin layer B on the surface of the foamed resin layer facing the surface protective layer.

10. The laminate sheet according to any one of claims 1 to 9, wherein the laminate sheet has an embossed pattern on an outermost surface of the laminate sheet that faces the surface protective layer relative to the base layer.

11. The laminate sheet according to any one of claims 1 to 10, further comprising a decorative layer between the substrate layer and the surface protective layer.

12. The laminate sheet according to any one of claims 1 to 11, wherein the laminate sheet is a decorative wall sheet.

13. The laminate sheet according to any one of claims 1 to 11, wherein the laminate sheet is a decorative floor sheet.

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