Films or sheets and laminates using these

Abstract

To provide a weather-resistant laminate that comprises an antiviral or antibacterial film composed of a monovalent copper compound or the like and a nonwoven fabric or a woven fabric.SOLUTION: A film or sheet comprises a resin (A), at least one compound (B) selected from the group consisting of a monovalent copper compound and an iodide of iodine and an element of Periods 4 to 6 and Groups 8 to 15 in the periodic table, and an antioxidant (C). The film or sheet is laminated with a nonwoven fabric or a woven fabric to form a laminate.

Description

[Technical Field]

[0001] The present invention relates to an antiviral or antibacterial film or sheet that can inactivate various viruses and bacteria attached thereto, regardless of whether they have an envelope or not, and even in the presence of lipids or proteins, and to a laminate using the same. [Background technology]

[0002] An antiviral or antibacterial adhesive tape is known in which an antiviral or antibacterial layer containing a resin and particles of at least one monovalent copper compound that acts as an antiviral or antibacterial agent is arranged so as to be in contact with the outside air (see Patent Document 1).

[0003] Also known is a laminate film having an antiviral coating film formed on at least one surface using an antiviral coating film-forming paint containing at least one compound selected from the group consisting of polyfunctional (meth)acrylates, monovalent copper compounds, and iodides containing iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an amine compound (see Patent Document 2). Furthermore, Patent Document 2 describes that it can be added as an optional component to the antiviral coating film-forming paint.

[0004] Also known is a laminate having a cured layer formed by curing a photocurable anti-fogging resin composition having antiviral or antibacterial properties, which contains an acrylic binder, a monovalent copper compound, and a photopolymerization initiator, on a substrate (see Patent Document 3). Furthermore, Patent Document 3 describes that additives such as antioxidants can be used in combination with the resin composition as needed, as long as the performance is not impaired. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-88916 [Patent Document 2] International Publication No. 2020-203069 [Patent Document 3] Patent No. 6830172 Summary of the Invention [Problem to be solved by the invention]

[0006] When an antiviral or antibacterial film made of a monovalent copper compound or the like is laminated with a nonwoven fabric or a woven fabric to obtain a laminate, there has been a problem in that the weather resistance is significantly inferior in terms of antiviral activity.

[0007] An object of the present invention is to provide an antiviral or antibacterial film comprising a monovalent copper compound or the like, and a laminate comprising the antiviral or antibacterial film and a nonwoven fabric or a woven fabric, which has weather resistance and antiviral activity. [Means for solving the problem]

[0008] As a result of intensive research to achieve the above-mentioned objects, the present inventors have found that by adding an antioxidant in advance to an antiviral or antibacterial film made of a monovalent copper compound or the like, it is possible to obtain a weather-resistant film, sheet, or laminate while maintaining antiviral activity or antibacterial activity, and have thereby completed the present invention.

[0009] That is, the present invention is specified by the following items. [1] The film or sheet of the present invention contains a resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds, iodine, and iodides of elements of Periods 4 to 6 and Groups 8 to 15 of the periodic table, and an antioxidant (C). [2] A laminate in which a film or sheet containing a resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodine and iodides of elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C) is disposed on a nonwoven fabric or woven fabric. [3] A laminate comprising a film or sheet containing a resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodine and iodides of elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C), and a resin layer (D) disposed between the film or sheet and a nonwoven or woven fabric. [4] The laminate according to [3], wherein the resin forming the resin layer (D) has an MFR (measured in accordance with JIS K 7210 at 190° C. and 2.16 kgf) of 3 to 15 g / 10 min. [5] A laminate obtained by laminating a film or sheet containing a resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds, iodine, and iodides of elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C) with a nonwoven fabric or a woven fabric. [6] The laminate according to [5], wherein the lamination is extrusion lamination or dry lamination. [7] The film, sheet or laminate according to any one of [1] to [6], wherein the film or sheet contains 0.1 to 5.0% by mass of an antioxidant (C). [8] The film, sheet or laminate according to any one of [1] to [6], wherein the film or sheet contains 0.3 to 3.0% by mass of an antioxidant (C). [9] The film, sheet or laminate according to any one of [1] to [8], wherein the compound (B) is contained in the film or sheet in an amount of 1.5 to 2.0% by mass.

[10] The film, sheet or laminate according to any one of [1] to [9], wherein the resin (A) and the resin layer (D) are made of an olefin-based resin.

[11] A pressure-sensitive adhesive or cohesive laminate comprising a pressure-sensitive adhesive or cohesive layer on the side of the nonwoven or woven fabric of the laminate according to any one of [2] to

[10] opposite to the side on which the film or sheet is placed. [Effects of the Invention]

[0010] The film, sheet or laminate of the present invention has the effect of being able to exhibit weather resistance in terms of antiviral or antibacterial activity. DETAILED DESCRIPTION OF THE INVENTION

[0011] The film or sheet of the present invention contains a resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodides of iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C).

[0012] The resin (A) used in the present invention is not particularly limited as long as it is a resin that can appropriately disperse the compound (B) and the antioxidant (C). Specifically, the resin (A) may be a thermoplastic resin, a thermosetting resin, or a radiation-curable resin that is cured by irradiation with electron beams, ultraviolet rays, or the like. The resin used for the resin (A) may be a combination of two or more types.

[0013] When considering the production of a laminate by laminating with a nonwoven fabric or a woven fabric, a thermoplastic resin is preferred as the resin used for Resin A. Specific examples of resins used for Resin A in such cases include olefin-based resins such as polypropylene, polyethylene, and ethylene-propylene random copolymer; aliphatic polyester resins such as polylactic acid, polycaprolactone, and polybutylene succinate; polyester resins such as aromatic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; polystyrene resins, acrylic resins, polyamide resins, polycarbonate resins, polyacetate resins, and ABS resins. From the viewpoints of moldability and reduced manufacturing costs, the resin used for Resin A is preferably an olefin-based resin or polyester resin, more preferably an olefin-based resin, with polyethylene resins and polypropylene resins being even more preferred, and low-density polyethylene resins being even more preferred.

[0014] The compound (B) used in the present invention is at least one compound selected from the group consisting of monovalent copper compounds and iodides formed from iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table.

[0015] Specific examples of monovalent copper compounds include chlorides, acetates, sulfides, iodides, bromides, peroxides, oxides, and thiocyanides. Preferred examples of monovalent copper compounds include cuprous chloride, cuprous acetate, cuprous bromide, cuprous iodide, cuprous thiocyanate, cuprous sulfide, and cuprous oxide. These compounds can be used alone or in combination of two or more.

[0016] Specific examples of elements in periods 4 to 6 and groups 8 to 15 of the periodic table include Cu, Ag, Sb, Ir, Ge, Sn, Tl, Pt, Pd, Bi, Au, Fe, Co, Ni, Zn, In, and Hg. Specific examples of iodides of these elements include CuI, AgI, SbI3, IrI4, GeI4, GeI2, SnI2, SnI4, TlI, PtI2, PtI4, PdI2, BiI3, AuI, AuI3, FeI2, CoI2, NiI2, ZnI2, HgI, and InI3. These elements can be used alone or in combination of two or more.

[0017] Suitable examples of compound (B) include CuI, AgI, SnI4, CuCl, CuBr, and CuSCN, which have excellent storage stability in air and can be used alone or in combination of two or more.

[0018] In the present invention, the form of compound (B) is not particularly limited, but it is preferably used as particles. The particle size of compound (B) is not particularly limited, but it is preferably fine particles with an average particle size of 500 μm or less. In consideration of particle production, handling, and chemical stability, it is preferable that the particle size of compound (B) is 1 nm or more. In this specification, the average particle size refers to the volume average particle size.

[0019] The content of compound (B) in the film or sheet of the present invention is not particularly limited as long as it is an amount that can sufficiently exert antibacterial or antiviral activity. In consideration of the balance between the strength and durability of the film or sheet and the antibacterial or antiviral activity, the content of compound (B) in the film or sheet is preferably in the range of 0.5 to 10.0 mass%, more preferably in the range of 0.8 to 5.0 mass%, more preferably in the range of 1.0 to 2.5 mass%, and particularly preferably in the range of 1.5 to 2.0 mass%.

[0020] Specific examples of the antioxidant (C) used in the present invention include aromatic amine antioxidants, hindered phenol antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, etc. These can be used alone or in combination of two or more.

[0021] Specific examples of aromatic amine antioxidants include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, 4-isopropoxydiphenylamine, etc. Among these, diphenylamine compounds are preferred examples of aromatic amine antioxidants.

[0022] Specific examples of the hindered phenol antioxidant include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, and 2,2'-methylene-bis(4-ethyl-6-t-butylphenol). ol), 4,4'-methylene-bis(6-t-butyl-o-cresol), 4,4'-methylene-bis(2,6-di-t-butylphenol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 4,4'-thiobis(6-t-butyl-o-cresol), 2,2'-thiobis(4-methyl-6-t-butylphenol) phenol), 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzenesulfonic acid, 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyl-diphenylmethane, α-octadecyl-3(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 6-(hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, hexamethyl glycol-bis[β-(3,5-di-t-butyl-4-hydroxyphenol)propionate], N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate], dioctadecyl ester of 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples of suitable antioxidants include 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-di-t-butylphenyl)butane, tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate, and tris[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl]isocyanurate. Among these, preferred examples of hindered phenol antioxidants include those with a molecular weight of 500 or more, such as tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane.

[0023] More specific examples of such phenolic antioxidants include "Irganox 1010" (registered trademark, the same applies hereinafter) and "Irganox 1076" manufactured by BASF Japan Ltd., and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by ADEKA Corporation.

[0024] Specific examples of sulfur-based antioxidants include thioether-based, dithioacid salt-based, mercaptobenzimidazole-based, thiocarbanilide-based, and thiodipropionate-based compounds, etc. Among these, preferred examples of sulfur-based antioxidants include thiodipropionate-based compounds.

[0025] Specific examples of phosphorus-based antioxidants include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid, metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate, phosphates of Group 1 or Group 12 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate, phosphate compounds, phosphite compounds, and phosphonite compounds. Among these, phosphite compounds are preferred examples of phosphorus-based antioxidants.

[0026] Specific examples of the phosphite compound include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mono / dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butyl-4-methylphenyl)pentaerythritol phosphite, bis(2,6-di Examples of the tert-butylphenyl diphosphite include bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butylphenyl)octyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphite, and 6-[3-(3-tert-butyl-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]-dioxaphosphepine. Among these, preferred examples of the phosphite compound include triphenyl phosphite, tris(mononylphenyl) phosphite, and tris(2,4-di-tert-butylphenyl) phosphite, and more preferred example is tris(2,4-di-tert-butylphenyl) phosphite.

[0027] More specific examples of such phosphite compounds include "ADK STAB 1178" manufactured by ADEKA CORPORATION, "SUMIRAIZER TNP" manufactured by Sumitomo Chemical Co., Ltd., "JP-351" manufactured by Johoku Chemical Industry Co., Ltd., "ADK STAB 2112" manufactured by ADEKA CORPORATION, "IRGAFOS 168" manufactured by BASF, and "JP-650" manufactured by Johoku Chemical Industry Co., Ltd.

[0028] Particularly preferred phosphite compounds include those having a pentaerythritol diphosphite structure, such as bis(2,4-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite. More specific examples of such phosphite compounds include "ADEKA STAB PEP-36" manufactured by ADEKA Corporation and "Doverphos S-9228" manufactured by Dover Chemical.

[0029] The content of the antioxidant (C) used in the present invention in the film or sheet is not particularly limited. Considering the balance between the efficacy as an antioxidant and the strength, durability, and antibacterial or antiviral activity of the film or sheet, the content of the antioxidant (C) in the film or sheet is preferably in the range of 0.1 to 5.0 mass%, more preferably in the range of 0.5 to 3.0 mass%, and even more preferably in the range of 0.5 to 1.0 mass%.

[0030] The thickness of the film or sheet of the present invention is not particularly limited and can be any thickness as desired. In consideration of antibacterial or antiviral properties, weather resistance, and scratch resistance, the thickness of the film or sheet of the present invention is preferably in the range of 10 to 100 μm, more preferably in the range of 10 to 60 μm, and even more preferably in the range of 15 to 55 μm. If it is less than 10 μm, processing is difficult.

[0031] The method for producing the film or sheet of the present invention is not particularly limited, and examples thereof include ordinary film or sheet molding methods. A more specific example of a method for producing the film or sheet of the present invention will be given below.

[0032] Masterbatch pellets of resin (A) containing a high concentration of compound (B) are prepared in advance. These masterbatch pellets are mixed with antioxidant and resin (A) pellets at a certain ratio, followed by melt-kneading to produce pellets that serve as the raw material for the film or sheet of the present invention. The masterbatch pellets can also be mixed with antioxidant and resin (A) pellets at a certain ratio, followed by melt-kneading to form a film or sheet without pelletizing.

[0033] Compound (B) is pulverized into nano-order particles, for example, using a jet mill, hammer mill, ball mill, vibration mill, bead mill, etc. The pulverization method is not particularly limited, and both dry and wet methods can be used.

[0034] In the method for producing the masterbatch pellets, first, the compound (B) obtained by pulverization is mixed with pellets of the resin (A). The resulting mixture is then fed to a kneading extruder, and the compound (B) is uniformly incorporated into the resin (A) and kneaded. The resulting kneaded mixture is cooled and then finely cut using a pelletizer to obtain masterbatch pellets containing a high concentration of the compound (B).

[0035] Next, masterbatch pellets containing a high concentration of compound (B), antioxidant (C), and resin (A) pellets are mixed so that the compound (B) is present in a predetermined ratio. The resulting pellets are melt-kneaded. The melt-kneaded mixture is then pelletized in the same manner as above, or formed into a film or sheet using a T-die method, inflation method, calendaring method, or the like, either as is or in the melt-kneaded state. This allows for the production of an antiviral or antibacterial film or sheet of the present invention in which compound (B) and antioxidant (C) are uniformly dispersed in resin (A).

[0036] In addition, in the stage of preparing the masterbatch pellets, the antioxidant (C) may be added together with the compound (B) to prepare masterbatch pellets containing the compound (B) and the antioxidant (C).

[0037] The film or sheet of the present invention may further contain functional substances other than the compound (B) and the antioxidant (C) to the extent that the functionality of the film or sheet of the present invention is not impaired. Specific examples of such functional substances include other antiviral agents, other antibacterial agents, antifungal agents, antiallergens, plasticizers, desiccants, hardeners, antiskinning agents, flattening agents, anti-sagging agents, heat absorbers, lubricants, surfactants, dispersants, thickeners, viscosity adjusters, stabilizers, drying adjusters, pigments, ultraviolet absorbers, catalysts, anti-reflection materials, etc.

[0038] The laminate of the present invention is a laminate in which the above-mentioned film or sheet is disposed on a nonwoven fabric or woven fabric. The nonwoven fabric used in the present invention is not particularly limited, and specific examples include nonwoven fabrics formed by the spunbond method (spunbond nonwoven fabric), nonwoven fabrics formed by the meltblown method (meltblown nonwoven fabric), nonwoven fabrics formed by the hydroentanglement method (spunlace nonwoven fabric), nonwoven fabrics formed by the needlepunch method, nonwoven fabrics formed by the heat fusion method (thermal bond nonwoven fabric), nonwoven fabrics formed by the solvent bonding method (chemical bond nonwoven fabric), and nonwoven fabrics formed by the carding method. Among these, spunbond nonwoven fabrics, spunlace nonwoven fabrics, and meltblown nonwoven fabrics are preferred from the viewpoint of good extensibility.

[0039] The material of the nonwoven fabric is not particularly limited, but is preferably a nonwoven fabric made of a thermoplastic elastomer, from the viewpoints of high elongation at break, flexibility, and the ability to be stretched with less force. Specific examples of such thermoplastic elastomers include olefin-based elastomers, styrene-based elastomers, urethane-based elastomers, and nylon-based elastomers. Weak adhesion between the nonwoven fabric layer and the resin layer (D) described below or the film or sheet of the present invention may cause delamination, resulting in loss of airtightness and watertightness. Therefore, it is preferable to select a material for the nonwoven fabric layer that has good adhesion to the resin layer (D) or the film or sheet of the present invention. Specifically, when a polyolefin resin is selected for the resin layer (D) or the film or sheet of the present invention, it is preferable to use an olefin-based elastomer or a styrene-based elastomer for the nonwoven fabric.

[0040] Or the basis weight of the nonwoven fabric (representing the mass per unit area) is 15 to 100 g / m 2 The range is preferably 20 to 60 g / m 2 It is more preferable that the thickness is 100 g / m 2 If it is larger, the workability is poor and it is 15 g / m 2 If the thickness is less than this, sufficient strength may not be obtained.

[0041] The woven fabric used in the present invention is preferably a woven fabric made using drawn yarn. The material for the drawn yarn is preferably high-density polyethylene alone, or a mixture of up to 50% by mass of at least one resin selected from linear low-density polyethylene, branched low-density polyethylene, medium-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid alkyl ester copolymer, polypropylene, and propylene-ethylene copolymer.

[0042] The drawn yarn may be in the form of a monofilament, a multifilament, a flat yarn, or the like. In consideration of formability and flexibility, a flat yarn is preferred as the drawn yarn. The method for producing the drawn yarn is not particularly limited, and known techniques can be used.

[0043] Considering mechanical properties such as tensile strength and flexibility, the fineness of the drawn yarn is preferably in the range of 500 to 5000 decitex (dt), more preferably in the range of 1000 to 3000 dt.

[0044] The weft density of the woven fabric is preferably in the range of 30 to 60 warp threads / 2.54 cm and 10 to 30 weft threads / 2.54 cm. The ratio of warp threads to weft threads of the woven fabric is preferably in the range of 3 / 1 to 2 / 1. Specific examples of the weave of the woven fabric include plain weave, twill weave, leno weave, and twill weave.

[0045] More specifically, the warp yarns of the woven fabric used in the present invention have a melt flow rate of 5 to 50 g / 10 min and a density of 0.951 g / cm. 3 The warp yarns of the woven fabric used in the present invention may be composed of monofilaments made from a composition containing 50-95% by weight of high-density polyethylene having a melt flow rate of 2-50 g / 10 min and 5-50% by weight of low-density polyethylene having a melt flow rate of 2-50 g / 10 min. The ... 3 The present invention may also be a woven fabric or the like using drawn yarns obtained by inflation molding high-density polyethylene having a melt flow rate of 0.30 to 1.2 g / 10 min, a melt tension of 0.3 to 5 g, and a flow ratio of 10 to 60, followed by slitting and drawing.

[0046] The laminate of the present invention has a structure in which the film or sheet is disposed on the nonwoven fabric or woven fabric. In consideration of the adhesion between the nonwoven fabric or woven fabric and the film or sheet, it is preferable to provide a resin layer (D) between the nonwoven fabric or woven fabric and the film or sheet.

[0047] The resin constituting the resin layer (D) is preferably one that can adhere to both the nonwoven or woven fabric and the film or sheet. Specifically, the resin constituting the resin layer (D) is preferably a thermoplastic resin, and more specific examples thereof include olefin resins such as polypropylene, polyethylene, and ethylene-propylene random copolymers, aliphatic polyester resins such as polylactic acid, polycaprolactone, and polybutylene succinate, polyester resins such as aromatic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, polystyrene resins, acrylic resins, polyamide resins, polycarbonate resins, polyacetate resins, and ABS resins. Among these, from the viewpoint of having extensibility and good chemical resistance, olefin resins are preferred as the resin constituting the resin layer (D), and specific examples include low-density polyethylene, linear low-density polyethylene (including ethylene-α-olefin copolymers produced using a metallocene catalyst), high-density polyethylene, polypropylene, propylene-ethylene block copolymers, propylene-ethylene random copolymers, ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-vinyl alcohol copolymers (EVOH), etc. From the viewpoint of having appropriate flexibility and maintaining good permanent set, low-density polyethylene and linear low-density polyethylene are preferred examples of the resin constituting the resin layer (D).

[0048] The MFR (measured in accordance with JIS K 7210 at 190°C and 2.16 kgf) of the resin forming the resin layer (D) is not particularly limited, but is preferably in the range of 3 to 15 g / 10 min, more preferably 4 to 8 g / 10 min, or 5 to 7 g / min. If it is less than 3 g / 10 min or more than 15 g / 10 min, the processability during production of the laminate will be poor.

[0049] The method for producing the laminate of the present invention is not particularly limited, but a method in which the film or sheet is laminated onto the nonwoven fabric or woven fabric is preferred, and the laminate can be produced by either extrusion lamination or dry lamination.

[0050] When a resin layer (D) is provided between the film or sheet and the nonwoven fabric or woven fabric, examples of methods include a method in which the film or sheet is formed in advance and a resin that forms the resin layer (D) between the film or sheet and the nonwoven fabric or woven fabric is extrusion laminated, and a method in which the nonwoven fabric or woven fabric, the resin layer (D), and the film or sheet are superimposed in this order and heat-pressed to bond them.

[0051] There are no particular limitations on the viruses that can be inactivated by the film or sheet of the present invention, and various viruses can be inactivated regardless of the type of genome, whether they are enveloped, etc. For example, rhinovirus, poliovirus, rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, influenza A / B / C viruses, parainfluenza virus, mumps virus, measles virus, human metapneumovirus, respiratory syncytial virus, Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, hepatitis B and C viruses, eastern and western equine encephalitis virus, O'nyong-nyong virus, rubella virus, Lassa virus, Junin virus, Machupo virus, and Guinea pig virus can be inactivated. Examples include Anaritovirus, Sabia virus, Crimean-Congo hemorrhagic fever virus, sandfly fever, Hantavirus, Sin Nombre virus, rabies virus, Ebola virus, Marburg virus, bat lyssavirus, human T-cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, human porvovirus, polyomavirus, human papillomavirus, adenovirus, herpesvirus, varicella-zoster virus, Epstein-Barr virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, molluscipox virus, and parapox virus.

[0052] The laminate of the present invention can be made into a pressure-sensitive adhesive or adhesive laminate by further providing a pressure-sensitive adhesive or adhesive layer on the surface of the nonwoven or woven fabric opposite to the surface on which the film or sheet is placed.

[0053] The pressure-sensitive adhesive is not particularly limited, and specific examples thereof include acrylic resin-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, silicone resin-based pressure-sensitive adhesives, polyester resin-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, urethane resin-based pressure-sensitive adhesives, fluorine-based pressure-sensitive adhesives, and epoxy resin-based pressure-sensitive adhesives. Among these, acrylic resin-based pressure-sensitive adhesives are preferred in terms of weather resistance. The above pressure-sensitive adhesives can be used alone or in combination of two or more. The pressure-sensitive adhesive may have any form. Specific examples of pressure-sensitive adhesives include emulsion-type pressure-sensitive adhesives, solvent-type pressure-sensitive adhesives, hot-melt-type pressure-sensitive adhesives, and active energy ray-curable pressure-sensitive adhesives (such as ultraviolet-curable pressure-sensitive adhesives).

[0054] The adhesive is not particularly limited, and specific examples thereof include acrylic resin adhesives, α-olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin adhesives, epoxy resin adhesives, vinyl chloride resin adhesives, chloroprene rubber adhesives, vinyl acetate resin adhesives, cyanoacrylate adhesives, silicone adhesives, and styrene-butadiene rubber adhesives. The above adhesives can be used alone or in combination of two or more. The adhesive may be of any form. Specific examples of adhesives include emulsion-type adhesives, solvent-type adhesives, hot-melt adhesives, and active energy ray-curable adhesives (such as ultraviolet-curable adhesives). [Example]

[0055] The present invention will be described in detail below using examples, but the scope of the present invention is not limited to these examples. [Example]

[0056] A melt-kneaded mixture 1 for an antiviral layer was obtained by melt-kneading 18 mass% of a commercially available masterbatch containing copper (I) iodide powder (10 mass% Cufitec (registered trademark) manufactured by NBC Meshtech GmbH + 90 mass% low-density polyethylene 1 (LC621, Japan Polyethylene), 81.5 mass% low-density polyethylene 2 (LC621, Japan Polyethylene), and 0.5 mass% antioxidant (Irganox 1010, manufactured by BASF) so that the film would contain 1.8 mass% copper iodide and 0.5 mass% antioxidant (Irganox 1010, manufactured by BASF).

[0057] Using a T-die method, low-density polyethylene 3 (Japan Polyethylene, LC621) as the resin layer (D) and the above-mentioned molten kneaded product 1 as the antiviral layer were extrusion-laminated in this order onto a nonwoven fabric (Toyobo, Ekure 3201A) at a die temperature of 300°C, to obtain a laminate 1 having a resin layer (D) of 20 μm and an antiviral layer of 10 μm. [Example]

[0058] Laminate 2 was obtained by extrusion laminating onto a nonwoven fabric in the same manner as in Example 1, except that 1.0 mass% of an antioxidant (Irganox 1010, manufactured by BASF) and 81 mass% of low-density polyethylene 2 in the molten kneaded material 1 for the antiviral layer were used. [Example]

[0059] The same procedure as in Example 2 was carried out, except that Irgafos 168 (manufactured by BASF) was used as the antioxidant, to obtain a laminate 3.

[0060] [Comparative Example 1] A laminate 4 was obtained in the same manner as in Example 1, except that no antioxidant was used and the low-density polyethylene 2 in the molten kneaded material 1 for the antiviral layer was used at 82 mass %.

[0061] (Antiviral evaluation method) (Rating 1) The evaluation was conducted in accordance with the method specified in ISO 21702, and the antiviral activity value was determined. Influenza A virus was used as the virus. The test specimen was left to stand for two hours. The evaluation results are summarized in Table 1.

[0062] (Rating 2) The test piece was immersed in pure water at room temperature for 4 hours, and then the same test as in Evaluation 1 was carried out to determine the antiviral activity value. The evaluation results are summarized in Table 1.

[0063] (Rating 3) The test piece was placed in a sunshine weather meter (carbon arc, black panel temperature: 63°C ± 3°C) for 8 hours, and then a test similar to Evaluation 1 was conducted to determine the antiviral activity value. The evaluation results are summarized in Table 1.

[0064] [Table 1]

[0065] It was found that laminates 1 to 3 of Examples 1 to 3 of the present invention exhibited stable and high antiviral activity regardless of the type of antioxidant, whereas laminate 4 of Comparative Example 1 was significantly inferior in weather resistance and water resistance in terms of antiviral activity. Furthermore, for the laminates 1 to 3 of the examples, no change from the very pale yellow of the molten kneaded material 1 for the antiviral layer could be visually confirmed. In contrast, for the laminate 4 of Comparative Example 1, the color changed from the very pale yellow of the molten kneaded material 1 for the antiviral layer to a gray color slightly closer to whitish. The very light yellow color of molten mixture 1 for the antiviral layer is such that it can be seen through a white substrate when multiple layers are stacked together to form a film-like laminate, making the color difficult to see for laminates 1 to 3 of the examples. In contrast, laminate 4 of the comparative example discolored from the original color of molten mixture 1 for the antiviral layer to a gray color, which could detract from the aesthetic appearance depending on the application of the laminate. Furthermore, laminate 4 of the comparative example developed a dark gray color depending on the subtle degree of processing, and so the color stability was also poor. [Industrial Applicability]

[0066] The film, sheet or laminate of the present invention stably exhibits antibacterial or antiviral activity, and can treat the surface of various articles with antibacterial or antiviral properties simply by attaching it to the surface, making it useful as a public health product.

Claims

1. A laminate in which a film or sheet containing an olefin resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodides consisting of iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C) is placed on a nonwoven fabric or woven fabric.

2. A laminate comprising a film or sheet containing an olefin resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodides consisting of iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C), and a resin layer (D) further disposed between the film or sheet and nonwoven or woven fabric.

3. 3. The laminate according to claim 2, wherein the resin forming the resin layer (D) has an MFR (measured in accordance with JIS K 7210 at 190° C. and 2.16 kgf) of 3 to 15 g / 10 min.

4. A laminate obtained by laminating a film or sheet containing an olefin resin (A), at least one compound (B) selected from the group consisting of monovalent copper compounds and iodides consisting of iodine and elements of periods 4 to 6 and groups 8 to 15 of the periodic table, and an antioxidant (C) with a nonwoven fabric or woven fabric.

5. 5. The laminate according to claim 4, wherein the lamination is extrusion lamination or dry lamination.

6. 6. The laminate according to claim 1, wherein the film or sheet contains 0.1 to 5.0% by mass of an antioxidant (C).

7. 6. The laminate according to claim 1, wherein the film or sheet contains 0.3 to 3.0% by mass of an antioxidant (C).

8. The laminate according to any one of claims 1 to 7, wherein the compound (B) is contained in an amount of 1.5 to 2.0% by mass in the film or sheet.

9. A laminate according to claim 2 or 3, wherein the resin forming the resin layer (D) is an olefin-based resin.

10. A pressure-sensitive adhesive or cohesive laminate comprising a pressure-sensitive adhesive or cohesive layer provided on the nonwoven or woven fabric of the laminate according to any one of claims 1 to 9 opposite to the side on which the film or sheet is disposed.

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