Transparent resin film, decorative board, and method for manufacturing decorative board

Abstract

To provide a transparent resin film capable of having an excellent weather resistance in a recess part of a rugged shape of the transparent resin film even if the rugged shape is formed on a surface thereof in order to impart excellent designability, and in addition having a flame resistance.SOLUTION: A transparent resin film is for protecting a pattern layer laminated on one side of a substrate. The transparent resin film at least includes a surface protective layer and a transparent resin layer laminated, and has a rugged shape on a side of the surface protective layer. The thickness of a recess part of the rugged shape of the transparent resin film is 100 μm or more. The transparent resin film contains an ultraviolet light absorber and a flame retardant.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a transparent resin film, a decorative board using the transparent resin film, and a method for manufacturing the decorative board.

Background Art

[0002] In recent years, due to the spread of the inkjet printing method using an inkjet printer, even in decorative sheets used for building materials, decorative molded products, etc., it has become possible to handle multi-variety and small-lot production and print complex patterns (characters, numbers, figures, etc.) as the pattern layer. Furthermore, the inkjet printing method has the merit that the substrate to be printed is not limited to a film, and printing can also be performed on substrates having a flat plate, unevenness, or a curved surface. However, usually, since the pattern layer printed by the inkjet printing method is on the outermost surface of the substrate, the surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient, and it is necessary to laminate a transparent resin film on the surface of the pattern layer to protect the pattern layer. As such a transparent resin film, for example, Patent Document 1 discloses an overlaminate film in which a protective layer is provided on one surface of transparent polypropylene containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer, and an adhesive layer is provided on the other surface.

[0003] However, in the conventional transparent resin film, although the design property is improved by having an uneven shape, there is a variation in weather resistance due to the difference in thickness caused by the uneven shape, and the weather resistance may be inferior particularly in the thin film portion, leaving room for improvement. In particular, the pattern layer printed by the inkjet printing method uses a wide variety of inks, and this tendency is remarkable.

[0004] In addition, since such a transparent resin film is laminated on the surface of a building and used as a decorative board, it may be required to meet the requirement of being able to obtain a non-combustion certification, indicating that it is difficult to burn in the event of a fire. Here, the requirement for obtaining a non-combustion certification refers to the predetermined requirements regarding the total heat release, maximum heat release rate, cracks, and hole generation in the heat release test conforming to ISO5660-1, as defined in Article 2, Paragraph 9 of the Building Standards Law of Japan.

[0005] As a decorative sheet used for a decorative board that meets the above requirements, a decorative sheet in which a base material sheet, a transparent resin layer, and a surface protection layer are laminated in this order, with the thickness of each layer within a specific range and containing a flame retardant, has been proposed (see, for example, Patent Document 2).

[0006] Although the above-mentioned decorative sheet is also a decorative sheet with excellent non-combustibility, it has not been studied whether it is difficult for fire to spread on the decorative sheet on the base material during a fire. For members constructed on a horizontal plane such as floor decorative materials, it is also an important performance for ensuring the evacuation time that the spread of the area of the burning decorative sheet is suppressed and it is difficult for fire to spread, showing flame retardancy.

[0007] Therefore, it is desired to develop a transparent resin film that is excellent in weather resistance, difficult for fire to spread, and has excellent flame retardancy, especially in the thin film part.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention aims to provide a transparent resin film that can have excellent weather resistance even in the concave portions of the uneven shape of the transparent resin film, and further has flame retardancy, even when an uneven shape is formed on the surface to impart excellent design properties.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that in a transparent resin film, an uneven shape is provided on the opposite side of the side on which the pattern layer is laminated, and the concave portion of the uneven shape of the transparent resin film formed by the uneven shape has a predetermined thickness, and the transparent resin film contains an ultraviolet absorber and a flame retardant. Thus, even when an uneven shape is formed on the surface to impart excellent design properties to the transparent resin film, a transparent resin film excellent in weather resistance and further excellent in flame retardancy can be obtained, and the present invention has been completed.

[0011] The present invention is a transparent resin film for protecting a pattern layer laminated on one side of a base material, wherein the transparent resin film has at least a surface protection layer and a transparent resin layer laminated thereon, has an uneven shape on the surface protection layer side, the thickness of the concave portion of the uneven shape of the transparent resin film is 100 μm or more, and the transparent resin film is characterized by containing an ultraviolet absorber and a flame retardant.

[0012] In the transparent resin film of the present invention, it is preferable that the ultraviolet absorber is contained in the surface protection layer and / or the transparent resin layer. Further, the transparent resin film of the present invention preferably has an adhesive primer layer on the side opposite to the surface protection layer side of the transparent resin layer. Further, the adhesive primer layer preferably has a thickness of 0.5 μm or more and 10 μm or less. Further, the ultraviolet absorber is preferably a triazine-based ultraviolet absorber. Further, the transparent resin layer preferably contains a flame retardant. Further, the surface protective layer preferably contains a flame retardant. Further, the surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent. Further, the flame retardant is preferably at least one selected from the group consisting of metal phosphinate-based flame retardants, phosphazene-based flame retardants, and NOR type hindered amine-based flame retardants. Further, the transparent resin layer preferably contains a filler.

[0013] The present invention is also a decorative board characterized by comprising a base material, a pattern layer, and the transparent resin film of the present invention in this order in the thickness direction.

[0014] The decorative board of the present invention preferably has an adhesive layer between the pattern layer laminated on one side of the base material and the transparent resin film. The present invention is also a method for manufacturing the decorative board of the present invention, which comprises a step of forming an adhesive layer on the surface of the transparent resin film on the side laminated with the pattern layer, and a step of bonding the transparent resin film and the pattern layer via the adhesive layer.

Advantages of the Invention

[0015] The present invention can provide a transparent resin film that can impart excellent design properties to a decorative board and is also excellent in weather resistance and flame retardancy. The decorative board of the present invention using such a transparent resin film of the present invention has excellent design properties and is also excellent in weather resistance and flame retardancy.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0017] <Transparent resin film> First, the transparent resin film of the present invention will be described. The transparent resin film of the present invention has at least a surface protective layer and a transparent resin layer laminated thereon, has an uneven shape on the surface protective layer side, the thickness of the concave portion of the uneven shape is equal to or more than a predetermined value, and the transparent resin film contains an ultraviolet absorber and a flame retardant. In the conventional transparent resin film, a difference in thickness is caused by having an uneven shape, and in a portion where the film thickness is thin (the concave portion of the uneven shape) among them, the amount of the ultraviolet absorber becomes small, and sufficient weather resistance cannot be obtained. However, in the transparent resin film of the present invention, since the thickness of the concave portion of the uneven shape is sufficiently ensured and the concave portion of the uneven shape also contains an ultraviolet absorber, sufficient weather resistance can be obtained even in the thin film portion caused by the uneven shape, and since a flame retardant is contained, excellent flame retardancy can be obtained. In addition, in this specification, "the concave portion of the uneven shape also contains an ultraviolet absorber" means that in a cross-sectional view, an ultraviolet absorber exists between the bottom of the concave portion of the uneven shape of the transparent resin film of the present invention and the opposite side surface to the surface protective layer of the transparent resin film. Specifically, on the surface on the surface protective layer side of the transparent resin film of the present invention, a 10 cm 2 region including the concave portion of the uneven shape is cut out to prepare a sample, the sample prepared using a cryogenic mill is finely crushed, the ultraviolet absorber is extracted using THF (tetrahydrofuran), diluted using methanol, acetone, IPA, etc., and then, by measuring using a liquid chromatograph, it is possible to determine whether or not the concave portion of the uneven shape also contains an ultraviolet absorber.

[0018] A preferred example of the transparent resin film of the present invention will be described with reference to FIG. 1. As shown in FIG. 1, the transparent resin film 10 of the present invention has a transparent resin layer 12, has a surface protective layer 11 on one surface thereof, and has an uneven shape on the surface protective layer 11 side. By having such a surface protective layer 11, the transparent resin film 10 of the present invention has more excellent durability (scratch resistance, stain resistance, weather resistance, etc.), and can preferably prevent a decrease in design due to being damaged. Also, as shown in FIG. 2, the transparent resin film 10 of the present invention preferably has an adhesive primer layer 13 on the surface opposite to the surface protective layer 11 side of the transparent resin layer 12. From the viewpoint of making the adhesiveness between the transparent resin layer 12 and the surface protective layer 11 of the transparent resin film 10 of the present invention stronger, it is preferable to have a primer (not shown) between the transparent resin layer 12 and the surface protective layer 11. Hereinafter, each component of the transparent resin film of the present invention will be described.

[0019] (Transparent resin layer) The above-mentioned transparent resin layer is a layer that serves to protect the pattern layer laminated on one surface of the base material described later. As long as the above-mentioned transparent resin layer is transparent, it may be translucent or colored as long as the pattern layer described later can be visually recognized. The above-mentioned transparent resin layer contains one or more of the following resins, and is preferably made of a thermoplastic resin. Examples of the above-mentioned thermoplastic resin include olefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, and olefin-based thermoplastic elastomers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1,4-cyclohexanedimethanol copolymer, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, and methyl (meth)acrylate-styrene copolymer; polycarbonate resin, polyvinyl chloride, polystyrene, ionomer, etc. Among them, polypropylene is preferably used because of its high tensile strength, excellent chemical resistance, and excellent performance in the production process. In addition, in this specification, (meth)acrylate means acrylate or methacrylate.

[0020] The above-mentioned transparent resin layer may be unstretched, or may be uniaxially stretched or biaxially stretched as required. Also, the thickness of the above-mentioned transparent resin layer is not particularly limited, but the preferable lower limit is 20 μm, the preferable upper limit is less than 500 μm, the more preferable lower limit is 60 μm, and the more preferable upper limit is 420 μm or less. If the thickness of the above-mentioned transparent resin layer is less than 20 μm, the tensile strength may be insufficient and the surface of the above-mentioned pattern layer may not be protected. If it exceeds 500 μm, the transmittance of the transparent resin film of the present invention may decrease and the visibility of the pattern of the pattern layer may decrease.

[0021] The above-mentioned transparent resin layer may be composed of one layer, or may be a laminate composed of two or more layers.

[0022] In addition, when the transparent resin layer is a laminate composed of a plurality of layers, the types of resins constituting the layers to be formed may be the same or different, and the thicknesses of the layers composed of a plurality of resins may be the same or different. As a method for laminating two or more layers of the transparent resin layer, there is no limitation as long as it is a general method, and examples thereof include a dry lamination method and an extrusion thermal lamination method.

[0023] The transparent resin layer preferably contains a flame retardant. When the transparent resin layer is composed of a plurality of layers, it is effective for improving the flame retardancy that the layer closer to the surface protection layer contains a flame retardant.

[0024] Examples of the flame retardant include metal phosphinate-based flame retardants, phosphazene-based flame retardants, NOR-type hindered amine-based flame retardants, halogen-based flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants, phosphate ester-based flame retardants, and the like. Among them, from the viewpoint of the environment or the point that the transparency of the layer containing the flame retardant can be maintained while suppressing the addition amount, it is preferably at least one selected from the group consisting of metal phosphinate-based flame retardants, phosphazene-based flame retardants, and NOR-type hindered amine-based flame retardants. It has the property of trapping radicals generated from organic substances during combustion and making it difficult to continue combustion, and in terms of the effect of suppressing the spread of combustion in the horizontal combustion test, it preferably contains at least one selected from the group consisting of metal phosphinate-based flame retardants and phosphazene-based flame retardants. In terms of the effect of reducing the calorific value in the heat release test of ISO5660-1, the NOR-type hindered amine-based flame retardant is preferable.

[0025] Examples of the above-mentioned metal phosphinate flame retardants include aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanium tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanium tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), and titanium tetrakis(diphenylphosphinate). Examples of commercially available products of the above-mentioned metal phosphinate flame retardants include "EXOLITE OP-930", "EXOLITE OP-935", "EXOLITE OP-1230", "EXOLITE OP-1240", "EXOLITE OP-1312", etc. manufactured by Clariant Japan Co., Ltd.

[0026] Examples of the above-mentioned phosphazene flame retardants include cyclic and / or chain C such as phenoxyphosphazene, (poly)toloxyphosphazene (e.g., o-toloxyphosphazene, m-toloxyphosphazene, p-toloxyphosphazene, o,m-toloxyphosphazene, o,p-toloxyphosphazene, m,p-toloxyphosphazene, o,m,p-toloxyphosphazene, etc.), (poly)xylyloxyphosphazene, etc. 1-6 alkyl C 6-20 aryloxyphosphazene, and cyclic and / or chain C such as (poly)phenoxytoloxyphosphazene (e.g., phenoxy o-toloxyphosphazene, phenoxy m-toloxyphosphazene, phenoxy p-toloxyphosphazene, phenoxy o,m-toloxyphosphazene, phenoxy o,p-toloxyphosphazene, phenoxy m,p-toloxyphosphazene, phenoxy o,m,p-toloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, (poly)phenoxytoloxyxylyloxyphosphazene, etc. 6-20 aryl C 1-10 alkyl C 6-20Aryloxyphosphazenes and the like can be exemplified, and preferably cyclic and / or linear phenoxyphosphazenes, cyclic and / or linear C 1-3 alkyl C 6-20 aryloxyphosphazenes, C 6-20 aryloxy C 1-3 alkyl C 6-20 Aryloxyphosphazenes (for example, cyclic and / or linear trilyloxyphosphazenes, cyclic and / or linear phenoxytolylphenoxyphosphazenes, etc.) can be mentioned. Also, compounds having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), compounds having a crosslinked structure of 2,2-(4,4'-diphenylene)isopropylidene group, compounds having a crosslinked structure of 4,4'-oxydiphenylene group, compounds having a crosslinked structure of 4,4'-thiodiphenylene group, and the like, and compounds having a crosslinked structure of 4,4'-diphenylene group can also be mentioned.

[0027] Examples of the above NOR type hindered amine flame retardants include 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxyethylamino)-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; an oligomeric compound which is a condensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; an oligomeric compound which is a condensable product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)-6-chloro-s-triazine; the reaction product of peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, and N,N'-ethane-1,2-diylbis(1,3-propanediamine) (N,N',N'''-tris{2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)n-butylamino]-s-triazin-6-yl}-3,3'-ethylenediminodipropylamine); bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate; 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one; bis(1-stearyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, and the like.Examples of commercially available products of the above NOR type hindered amine flame retardants include Flamestab NOR116FF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, TINUVIN PA123 manufactured by BASF, LA-81 manufactured by ADEKA Corporation, and the like.

[0028] The above flame retardant may be used alone or in combination of two or more.

[0029] When the total mass of the above transparent resin layer is 100% by mass, the content of the above flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more. Also, when the total mass of the above transparent resin layer is 100% by mass, the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less. When the lower limit of the content of the above flame retardant is within the above range, the flame retardancy of the transparent resin film is further improved. Also, when the upper limit of the content of the above flame retardant is within the above range, the transparency of the transparent resin film is further maintained.

[0030] At least one of the above transparent resin layers may contain a filler. The above filler is not particularly limited as long as it does not impair the transparency of the transparent resin layer, and a filler having an average particle diameter equal to or less than the wavelength of visible light is preferable in that the sharpness of the decorative board using the transparent resin film (meaning the visibility of the pattern layer described later) is further improved. Examples of the filler include inorganic fillers such as silica, calcium carbonate, talc, and clay.

[0031] The above filler is preferably contained in at least one of the above transparent resin layers, and preferably contained in the same layer as the layer containing the flame retardant. That is, at least one of the above transparent resin layers preferably contains a flame retardant and a filler.

[0032] When at least one of the above transparent resin layers contains a flame retardant, it is preferable that the transparent resin layer further contains an inorganic filler having a polar group on the surface. By the transparent resin layer containing a flame retardant also containing an inorganic filler having a polar group on the surface, the flame retardancy of the transparent resin film and the sharpness of the decorative board using the transparent resin film are further improved. This is presumably because the polar part of the flame retardant is attracted to the polar group on the surface of the inorganic filler having a polar group, and the presence of the flame retardant on the surface improves the dispersibility. As the inorganic filler having a polar group on the surface, a hydrophilic inorganic filler can be used. For example, an inorganic filler having a hydroxyl group such as a silanol group on the surface can be mentioned. More specifically, hydrophilic silica can be used.

[0033] The silica used as the above filler may be either a natural product or a synthetic product, and may be either crystalline or amorphous. Also, the synthetic amorphous silica may be prepared by either a wet method or a dry method. The method for preparing the synthetic wet method silica prepared by the wet method is not particularly limited, and examples include the precipitation method and the gel method. The method for preparing the synthetic dry method silica prepared by the dry method is not particularly limited, and examples include the combustion method and the arc method. Silica is preferably silica having a small average particle diameter from the viewpoint that the sharpness of the decorative board using the transparent resin film is further improved, and fumed silica and hydrophilic fumed silica obtained by the combustion method are more preferable.

[0034] The BET specific surface area of the filler such as the above hydrophilic fumed silica is preferably 50 m 2 / g or more, more preferably 130 m 2 / g or more, and even more preferably 200 m 2More preferably, it is / g or more. When the lower limit of the BET specific surface area of the filler is within the above range, the average particle diameter is small, and in the case of hydrophilic fumed silica, the amount of silanol increases. Therefore, by adding the filler, the decrease in the transparency of the transparent resin layer is further suppressed, and the dispersibility of the flame retardant is further improved, and the flame retardancy of the transparent resin film and the sharpness of the decorative board using the transparent resin film are further improved. Further, when the lower limit of the BET specific surface area of the filler is within the above range, the flame retardancy of the transparent resin film is improved, and it becomes possible to reduce the content of the flame retardant.

[0035] In this specification, the BET specific surface area is the BET specific surface area measured by the nitrogen adsorption method according to the measurement method conforming to DIN66131.

[0036] As the hydrophilic fumed silica used as the above filler, commercially available products can be used. Examples of such commercially available products include AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, AEROSIL 380, etc. manufactured by Nippon Aerosil Co., Ltd.

[0037] When the above transparent resin layer contains a flame retardant and a filler, the content of the filler in the transparent resin layer is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and still more preferably 200 parts by mass or more with respect to 100 parts by mass of the flame retardant in the transparent resin layer. When the lower limit of the content of the filler in the transparent resin layer is within the above range, the sharpness of the decorative board using the transparent resin film is further improved. Further, the content of the filler in the thermoplastic resin layer is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.

[0038] The above transparent resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, ultraviolet (UV) treatment, and flame treatment within a range not departing from the gist of the present invention. Further, the above-mentioned transparent resin layer may further contain various additives such as a matting agent, a foaming agent, a lubricant, an antistatic agent, an antioxidant, a light stabilizer, a radical scavenger, and a soft component (e.g., rubber) so as to improve performance such as heat resistance and shrinkage rate.

[0039] (Surface protection layer) By having the above-mentioned surface protection layer, the durability (scratch resistance, stain resistance, weather resistance, etc.) of the transparent resin film of the present invention becomes more excellent, and it becomes possible to more suitably protect the surface of the pattern layer, and it is possible to preferably prevent a decrease in the design property due to damage to the transparent resin film itself of the present invention. In addition, the above-mentioned surface protection layer may have a single layer structure, a multi-layer structure composed of the same or different materials, or may be appropriately mixed with the materials shown below.

[0040] The above-mentioned surface protection layer is not particularly limited, and examples thereof include those composed of a crosslinked cured product of a two-component curable resin or an ionizing radiation curable resin composition. The crosslinked cured product is preferably transparent, and as long as it is transparent, it may be translucent or colored as long as the pattern layer described later can be visually recognized. As the above-mentioned two-component curable resin, the binder resin of the primer layer for adhesion described later may be used. As the above-mentioned ionizing radiation curable resin composition, for example, an oligomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule (hereinafter, also including so-called prepolymers, macromonomers, etc.) and / or a monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle having energy capable of polymerizing or crosslinking a molecule, and usually, an electron beam (EB) or ultraviolet rays (UV) is common.

[0041] Examples of the oligomer or monomer include compounds having a radically polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, and a cationically polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers can be used alone or in combination of two or more. In the present specification, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0042] Examples of the oligomer having a radically polymerizable unsaturated group in the molecule include oligomers such as urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, and triazine (meth)acrylate, and urethane (meth)acrylate oligomers are more preferably used. The molecular weight is usually about 250 to 100,000.

[0043] In addition, as the monomer having a radically polymerizable unsaturated group in the molecule, for example, a polyfunctional monomer is preferable, and a polyfunctional (meth)acrylate is more preferable. Examples of the polyfunctional (meth)acrylate include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate {5-functional (meth)acrylate}, dipentaerythritol hexa(meth)acrylate {6-functional (meth)acrylate}, and the like. Here, the polyfunctional monomer means a monomer having a plurality of radically polymerizable unsaturated groups.

[0044] In the present invention, it is more preferable that the above-described radiation-curable resin composition contains a radiation-curable resin component composed of a urethane acrylate oligomer and a polyfunctional monomer. As the radiation-curable resin component, it is particularly preferable that the mass ratio of urethane acrylate oligomer / polyfunctional monomer is 6 / 4 to 9 / 1. If it is within this mass ratio range, it can be made to have particularly excellent abrasion resistance. In addition, if necessary, in addition to the above-described radiation-curable resin component, a monofunctional monomer may be appropriately used within a range not contrary to the object of the present invention. Examples of the monofunctional monomer include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.

[0045] When crosslinking the above-described radiation-curable resin composition with ultraviolet rays, it is preferable to add a photopolymerization initiator to the radiation-curable resin composition. When the above-described radiation-curable resin composition is a resin system having a radically polymerizable unsaturated group, as the photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers, etc. can be used alone or in combination. Further, when the above-described radiation-curable resin composition is a resin system having a cationically polymerizable unsaturated group, as the photopolymerization initiator, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonic acid esters, etc. can be used alone or as a mixture. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the radiation-curable resin component.

[0046] In addition, various additives may be further added to the above-mentioned radiation-curable resin composition as required. Examples of these additives include thermoplastic resins such as urethane resin, polyvinyl acetal resin, polyester resin, polyolefin resin, styrene resin, polyamide resin, polycarbonate resin, acetal resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, and cellulose resin; lubricants such as silicone resin, wax, and fluororesin; ultraviolet absorbers such as benzotriazole, benzophenone, and triazine; light stabilizers such as hindered amine radical scavengers; matting agents, touch feeling modifiers such as silica, acrylic beads, and mica; and colorants such as dyes and pigments.

[0047] The above-mentioned flame retardant may be added to the surface protection layer. As the above-mentioned flame retardant, those described in the transparent resin layer can be appropriately selected and used, and it is preferably at least one selected from the group consisting of metal phosphinate-based flame retardants, phosphazene-based flame retardants, and NOR-type hindered amine-based flame retardants, and more preferably NOR-type hindered amine-based flame retardants. By adding a flame retardant to the surface protection layer, char formation and radical scavenging ability in combustion gases can be exhibited against the heat applied from the surface during combustion, so that the flammability can be reduced. The content of the flame retardant in the surface protection layer is preferably such that, with the total mass of the surface protection layer being 100% by mass, the lower limit of the content of the flame retardant is 3% by mass or more, more preferably 4.4% by mass or more, and the upper limit of the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less.

[0048] In addition, from the viewpoint of improving the flame retardancy of the transparent resin film while maintaining the sharpness of the decorative board using the transparent resin film, the surface protection layer preferably contains the flame retardant and the inorganic filler. As the above-mentioned inorganic filler, those described in the transparent resin layer can be appropriately selected and used, and silica is preferably used. Considering the dispersibility of the flame retardant, fumed silica is more preferably used, and among them, hydrophilic fumed silica is even more preferably used.

[0049] It is preferable that the surface protective layer contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent. By including the antibacterial agent and the antiviral agent in the surface protective layer, antibacterial properties and antiviral properties can be imparted to the transparent resin film. Moreover, by including the anti-allergen agent in the surface protective layer, anti-allergenic properties can be imparted to the transparent resin film.

[0050] The antibacterial agent and the antiviral agent can generally be roughly classified into organic and inorganic types. Examples of the organic antibacterial agent and antiviral agent include quaternary ammonium salt type, quaternary phosphonium salt type, pyridine type, pyrithione type, benzimidazole type, organic iodine type, isothiazoline type, anion type, ether type, and the like. Examples of the inorganic antibacterial agent and antiviral agent include those in which metal ions such as silver, copper, and zinc are supported on zeolite, apatite, zirconia, glass, molybdenum oxide, and the like. The antibacterial agent and the antiviral agent may be used alone or in combination of two or more.

[0051] Among the above-mentioned organic antibacterial agent and antiviral agent, an antibacterial agent and an antiviral agent of a benzimidazole-based compound or an anion-based compound that maintains a particle shape are preferably used. The above-mentioned "maintaining a particle shape" means that it exists in a particle state without dissolving in the radiation-curable resin composition that becomes the curable resin of the surface protective layer. Therefore, in the process of forming the surface protective layer, particles of the benzimidazole-based compound or particles of the anion-based compound are likely to float, and it is possible to easily unevenly distribute the particles of the benzimidazole-based compound or the particles of the anion-based compound on the outermost surface side of the surface protective layer. By unevenly distributing particles of a benzimidazole-based compound or particles of an anionic compound on the outermost surface side of the surface protective layer, it is possible to suppress the addition amount of antibacterial agents and antiviral agents necessary for obtaining predetermined antibacterial and antiviral properties, and thus it is easy to suppress a decrease in the scratch resistance of the surface protective layer.

[0052] As the anionic antibacterial agent and antiviral agent, those containing, for example, a styrene resin, a styrene polymer derivative compound, and an unsaturated carboxylic acid derivative compound are preferable. Further, the styrene polymer derivative compound and the unsaturated carboxylic acid derivative compound preferably contain at least one kind of structure among the structures of styrene, Na sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all the structures. This is because there are two types of viruses, with and without an envelope, and it is considered that the structures of antibacterial agents and antiviral agents that can effectively inhibit the activity against each are different. Therefore, for example, if only the effect on influenza virus, which is a non-enveloped virus, is expected, it may be sufficient to contain only a styrene polymer derivative compound, and in some cases, sufficient effects can be obtained by containing only a styrene resin alone.

[0053] As the inorganic antibacterial agent and antiviral agent, silver-based antibacterial agents and antiviral agents are preferable from the viewpoint of having no biological toxicity and excellent safety. Among them, phosphate-based glass silver-supported compounds, silver zeolite compounds, and molybdenum oxide silver double salt compounds are more preferable because they can exhibit antibacterial and antiviral properties even in a small amount, so the addition amount can be suppressed. The average particle diameter of the inorganic antibacterial agent and antiviral agent is preferably, for example, 0.1 to 10 μm. With the above average particle diameter, the antibacterial agent and antiviral agent can be preferably dispersed, and antibacterial and antiviral properties can be preferably imparted without unevenness.

[0054] When adding the above silver-based antibacterial agent or antiviral agent to the above surface protective layer, discoloration may occur depending on the surface protective layer (it may discolor due to heat or light in the state of the added paint, or may discolor due to heat or light after the formation of the above surface protective layer). In this case, it is possible to improve by adding an ultraviolet absorber, a light stabilizer, etc. in a timely manner. For example, when using a benzotriazole compound for the above molybdenum oxide silver double salt compound, a discoloration improvement effect can be expected.

[0055] The content of the above antibacterial agent or antiviral agent is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the radiation-curable resin.

[0056] The above anti-allergen agent contains at least one of an inorganic compound and an organic compound, and may be used alone or in combination of two or more. In addition, the above anti-allergen agent may have the above antibacterial agent or antiviral property.

[0057] The above inorganic compound is preferably a material carrying a metal. Examples of the material carrying the above metal include at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate and magnesium phosphate. Among them, titanium oxide, zirconium phosphate, etc. are preferable. The metal carried on the material carrying the above metal is preferably at least one selected from the group consisting of gold, silver, platinum, zinc and copper. Among them, silver, zinc, etc. are preferable. As commercially available products, for example, "Paraffin ANV-100: Silver supported on inorganic compound" manufactured by Ohara Palladium Co., Ltd., "Atom Ball TZ-R: Zinc supported on titanium oxide" manufactured by JGC Catalysts and Chemicals Ltd., etc. can be preferably used. This anti-allergen agent effectively acts against various allergens such as mites and pollen.

[0058] As the above organic compound, it is preferable that it is a polymer containing at least one monomer component selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, styrenesulfonic acid and its salts.

[0059] As the water-insoluble polymer containing a phenolic hydroxyl group, commercially available products such as "Arelbaster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Marcalinker M (trade name)" manufactured by Maruzen Oil Co., Ltd. can be used.

[0060] Examples of the polyphenol compound supported on an inorganic solid acid include those obtained by combining a polyphenol compound and a zirconium compound. Commercially available products thereof include "Arelimove (trade name)" manufactured by Toagosei Co., Ltd. These anti-allergen agents are effective against various allergens such as mites and pollen.

[0061] As the above styrenesulfonic acid and its salts, materials as shown in Patent No. 6136433 can be used. Preferred examples include a homopolymer of styrenesulfonate, a styrenesulfonate-styrenesulfonic acid copolymer, a styrenesulfonate-styrene copolymer, a styrenesulfonic acid-styrene copolymer, and a styrenesulfonate-styrenesulfonic acid-styrene terpolymer.

[0062] The above anti-allergen agent may be a mixture of an organic compound and an inorganic compound. For example, a mixture of an anionic phenolic material and a zinc-based material having anti-allergenic properties can be mentioned.

[0063] Examples of the anionic phenolic materials include tannin, tannic acid - tartar emetic, phenolsulfonic acid formaldehyde resin, sulfone compounds of novolak resins, methanesulfonic acid of novolak resins, methanesulfonic acid of resol resins, benzylated phenolsulfonic acid, thiophenol - based compounds, di - hydroxy, di - phenylsulfone - based compounds, ligand compounds, and metal chelate compounds thereof, etc.

[0064] The above - mentioned zinc - based materials are appropriately selected from water - soluble zinc compounds or water - insoluble zinc compounds, zinc / metal oxide composite materials, etc. Water - dispersed are composite particles of water - insoluble zinc compounds and / or water - insoluble zinc - metal oxides, with an average particle diameter of 50 μm or less, and it is preferable that the above - mentioned metal oxide contains at least one of titania, silica, and alumina.

[0065] The content of the above - mentioned anti - allergen agent is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the radiation - curable resin.

[0066] As the electron beam source of the ionizing radiation, for example, various electron beam accelerators such as the Cockcroft - Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, or linear type, Dynamitron type, high - frequency type, etc. can be used, and those that irradiate electrons with an energy of 70 to 1000 keV can be used. Also, the irradiation dose of the electron beam is preferably about 1 to 10 Mrad, for example. As the ultraviolet source of the above - mentioned ionizing radiation, for example, light sources such as ultra - high - pressure mercury lamps, high - pressure mercury lamps, low - pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. can be used, and the wavelength of the above - mentioned ultraviolet rays is mainly in the wavelength range of usually 190 to 380 nm.

[0067] Although the thickness of the above surface protective layer is not particularly limited, the preferable lower limit is 0.1 μm, the preferable upper limit is 50 μm, the more preferable lower limit is 1 μm, and the more preferable upper limit is 30 μm. If the thickness of the above surface protective layer is less than 0.1 μm, sufficient durability (scratch resistance, stain resistance, weather resistance, etc.) may not be imparted. If it exceeds 50 μm, the transmittance of the transparent resin film of the present invention may decrease and the visibility of the pattern of the pattern layer may decrease.

[0068] The above surface protective layer is a layer provided on the side opposite to the side laminated on the pattern layer described later, and is preferably adhered to the above transparent resin layer via a primer. By using the above primer, the adhesiveness between the above surface protective layer and the above transparent resin layer can be made stronger. As the above primer, the same ones as the adhesive primer layer described later can be preferably used.

[0069] (Uneven shape) The transparent resin film of the present invention has an uneven shape on the above surface protective layer side. The method for forming the above uneven shape is not particularly limited, and examples thereof include embossing by heat and a method of transferring an uneven shape by a shaping sheet. Examples of embossing by heat include a method of performing embossing using a well-known sheet-fed or rotary embossing machine. Examples of the embossed pattern include sandblasting, hairline, satin finish, wood grain plate conduit groove, slate surface unevenness, cloth surface texture, and ten thousand line grooves. Also, the temperature during embossing is not particularly limited, but a temperature at which so-called embossing return, in which the uneven pattern disappears during heat pressure bonding molding, is reduced is preferable. Also, the depth of the uneven shape to be formed is not particularly limited, but for example, it is preferably adjusted as appropriate so that the center line average roughness Ra defined in JIS B 0601 (1982) is within the range of 1 to 30 μm.

[0070] The thickness of the transparent resin film of the present invention is not particularly limited, but the thickness of the concave portion of the concavo-convex shape is 100 μm or more. If the thickness of the concave portion of the concavo-convex shape of the transparent resin film is less than 100 μm, sufficient durability (abrasion resistance performance, scratch resistance) cannot be imparted to the transparent resin film of the present invention, and the amount of the ultraviolet absorber contained in the concave portion of the concavo-convex shape becomes insufficient, and sufficient weather resistance cannot be obtained. The thickness of the concave portion of the concavo-convex shape is preferably 105 μm or more and 480 μm or less, and more preferably 110 μm or more and 300 μm or less. Further, the transparent resin film of the present invention contains an ultraviolet absorber in the concave portion of the concavo-convex shape. Here, the "concave portion of the concavo-convex shape" refers to the thinnest portion of the thickness of the transparent resin film of the present invention, and as shown in FIG. 1, it is a portion including the deepest concave portion of the concavo-convex shape of the surface protective layer 11, and can be confirmed by microscopic observation of the cross section of the transparent resin film of the present invention. Note that the length from the bottom of the deepest concave portion to the opposite side surface from the surface protective layer 11 side of the transparent resin layer 12 is the "thickness of the concave portion of the concavo-convex shape". The upper limit of the thickness of the concave portion of the concavo-convex shape of the transparent resin film is not particularly limited, but for example, it is preferably less than 500 μm. Further, as shown in FIG. 1, the length from the surface of the surface protective layer 11 to the opposite side surface from the surface protective layer 11 side of the transparent resin layer 12 is the total thickness of the transparent resin film 10 of the present invention, and the preferable lower limit of the total thickness is 100 μm, the preferable upper limit is 500 μm, the more preferable lower limit is 140 μm, and the more preferable upper limit is 460 μm.

[0071] (Ultraviolet absorber) The transparent resin film of the present invention contains an ultraviolet absorber. As the ultraviolet absorber, for example, an organic or inorganic ultraviolet absorber can be used. Among them, an organic ultraviolet absorber having excellent transparency is preferably used. Examples of the above-mentioned organic ultraviolet absorbers include 2' - hydroxyphenyl - 5 - chlorobenzotriazole - type ultraviolet absorbers such as 2 - (2'-hydroxy - 3',5'-di - tert - butylphenyl)-5 - chlorobenzotriazole, 2 - (2'-hydroxy - 3'-tert - butyl - 5'-methylphenyl)-5 - chlorobenzotriazole, 2 - (2'-hydroxy - 3'-tert - amyl - 5'-methylphenyl)-5 - chlorobenzotriazole, 2 - (2'-hydroxy - 3'-isobutyl - 5'-methylphenyl)-5 - chlorobenzotriazole, 2 - (2'-hydroxy - 3'-isobutyl - 5'-propylphenyl)-5 - chlorobenzotriazole; benzotriazole - type ultraviolet absorbers such as 2' - hydroxyphenylbenzotriazole - type ultraviolet absorbers like 2 - (2'-hydroxy - 3',5'-di - tert - butylphenyl)benzotriazole, 2 - (2'-hydroxy - 5'-methylphenyl)benzotriazole; benzophenone - type ultraviolet absorbers such as 2,2'-dihydroxybenzophenone - type ultraviolet absorbers like 2,2'-dihydroxy - 4 - methoxybenzophenone, 2,2'-dihydroxy - 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy - 4,4'-tetrahydroxybenzophenone, and 2 - hydroxybenzophenone - type ultraviolet absorbers such as 2 - hydroxy - 4 - methoxybenzophenone, 2,4 - dihydroxybenzophenone; and salicylic acid ester - type ultraviolet absorbers such as phenyl salicylate, 4 - t - butyl - phenyl - salicylate. Among them, triazine - type ultraviolet absorbers are preferred from the viewpoints of suitably imparting weather resistance, designability, bleed suppression, etc.

[0072] Examples of the triazine-based ultraviolet absorber include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, tris(2-ethylhexyl) 4,4’,4’’-(1,3,5-triazine-2,4,6-triyltriimino)trisbenzoate, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, N,N’,N’’-tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and the like. In addition, a reactive ultraviolet absorber obtained by introducing an acryloyl group or a methacryloyl group into a benzotriazole skeleton can also be used. Alternatively, when high transparency is not required, an inorganic ultraviolet absorber can also be added. Examples of the inorganic ultraviolet absorber include titanium oxide, cerium oxide, iron oxide, zinc oxide, etc. having a particle size of 0.2 μm or less.

[0073] The content of the above ultraviolet absorber is appropriately determined according to the ultraviolet absorption ability of the ultraviolet absorber used. For example, when a triazine-based ultraviolet absorber is contained in the transparent resin layer as the above ultraviolet absorber, it is preferably 1% by mass or more and 10% by mass or less in the transparent resin layer. If the content in the transparent resin layer is less than 1% by mass, the weather resistance may not be sufficiently imparted. If the content in the transparent resin layer exceeds 10% by mass, the transparency of the film may be impaired, the design property may be reduced when used as a decorative board, the adhesion between the transparent resin film of the present invention and the pattern layer described later may not be sufficiently obtained, and the processability of the transparent resin film of the present invention may be reduced. The more preferable lower limit of the content of the above ultraviolet absorber is 2% by mass, and the more preferable upper limit is 7% by mass.

[0074] Since the transparent resin film of the present invention can have extremely excellent weather resistance, it is preferable that the above ultraviolet absorber is contained in the above surface protective layer and / or the above transparent resin layer. In addition, in the conventional transparent resin film, when an ultraviolet absorber is contained in a layer having an uneven shape, there are portions where the amount of the ultraviolet absorber is small due to the difference in thickness, so there are portions where sufficient weather resistance cannot be obtained. However, in the transparent resin film of the present invention, as described above, the concave portion of the uneven shape has a predetermined thickness, and the ultraviolet absorber is sufficiently contained even in the concave portion of the uneven shape, so high weather resistance can be obtained. Further, when the above-described primer layer is provided between the transparent resin layer and the surface protective layer, the primer layer may contain an ultraviolet absorber.

[0075] (Adhesive primer layer) As shown in FIG. 2, the transparent resin film of the present invention preferably has an adhesive primer layer 13 on the side opposite to the surface protective layer 11 side of the transparent resin layer 12. The above adhesive primer layer is a layer provided to strengthen the adhesiveness with the transparent resin film of the present invention laminated via an adhesive layer to a substrate provided with a pattern layer described later.

[0076] The above adhesive primer layer preferably contains a binder resin. Examples of the above binder resin include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose-based resin, polyester resin, vinyl chloride-vinyl acetate copolymer, etc. Urethane resin is preferable in terms of adhesiveness with the adhesive layer described later and production efficiency.

[0077] The above-mentioned primer layer for adhesion preferably has a thickness of 0.5 μm or more and 10 μm or less. If it is 0.5 μm or more, the adhesion between the transparent resin film of the present invention and the substrate laminated with the pattern layer described later can be suitably ensured. If it is 10 μm or less, the transparent resin film of the present invention does not become too thick, sufficient transparency can be obtained, and the design property of the decorative board can be suitably ensured. More preferably, the above-mentioned primer layer for adhesion has a thickness of 0.8 μm or more and 6 μm or less. In addition, the above-mentioned primer layer for adhesion may contain inorganic fine particles such as silica.

[0078] In the present invention, within a range not departing from the gist of the present invention, the above-mentioned transparent resin layer may be subjected to surface treatments such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma treatment, ultraviolet (UV) treatment, and flame treatment.

[0079] It is preferable that various additives (such as inorganic fillers added to the primer layer and the surface protection layer) added to each layer of the above-mentioned transparent resin film are vesiculated. The method for vesiculating various additives is not particularly limited, and vesiculation can be carried out by known methods. Among them, the supercritical reverse phase evaporation method is preferable.

[0080] Other examples of the above-mentioned vesiculation treatment method include the Bangham method, the extrusion method, the hydration method, the reverse phase evaporation method, the freeze-thaw method, etc. Briefly explaining such a vesiculation treatment method, in the above-mentioned Bangham method, chloroform or a chloroform / methanol mixed solvent is put into a container such as a flask, and further phospholipids are put in and dissolved. Then, the solvent is removed using an evaporator to form a thin film made of lipids. After adding a dispersion liquid of additives, vesicles are obtained by hydrating and dispersing with a vortex mixer. The above-mentioned extrusion method is a method of preparing a thin film phospholipid solution and passing it through a filter instead of the mixer used as an external perturbation in the above-mentioned Bangham method to obtain vesicles. The above hydration method is almost the same as the above Bangham method, but it is a method of gently stirring and dispersing without using a mixer to obtain vesicles. The above reverse evaporation method is a method of dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to form a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The above freeze-thaw method is a method that uses cooling and heating as external perturbations, and vesicles are obtained by repeating this cooling and heating.

[0081] Hereinafter, the supercritical reverse evaporation method will be described in detail. The above supercritical reverse evaporation method is a method in which an aqueous phase containing various additives as water-soluble or hydrophilic encapsulating substances is added to a mixture in which a substance forming the outer membrane of vesicles is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure conditions above the supercritical point, and a capsule-shaped vesicle containing various additives as encapsulating substances is formed with a single layer of membrane. Note that supercritical carbon dioxide means carbon dioxide in a supercritical state at or above the critical temperature (30.98 °C) and critical pressure (7.3773 ± 0.0030 MPa), and carbon dioxide under temperature or pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, single-layer lamellar vesicles with a diameter of 50 to 800 nm can be obtained. Generally, vesicles are a general term for those that contain a liquid phase inside vesicles having a spherical shell-like closed membrane structure. In particular, those whose outer membrane is composed of biological lipids such as phospholipids are called liposomes.

[0082] Examples of the phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0083] As the substance constituting the outer membrane, a nonionic surfactant or a dispersant such as a mixture of this and cholesterol or triacylglycerol can also be used.

[0084] Examples of the nonionic surfactant include one or more of polyglycerol ether, dialkyl glycerol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethyl ethylene copolymer, and polyoxyethylene-polycaprolactam copolymer.

[0085] Examples of the cholesterol include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, and colecalciferol.

[0086] The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the cosmetic sheet of the present invention, by using a liposome having an outer membrane formed from a phospholipid, the compatibility between the resin composition which is the main component of each layer and various additives can be made good.

[0087] <Cosmetic plate> The transparent resin film of the present invention is used to protect the above-mentioned pattern layer and further has an uneven shape on the surface, so it can also impart excellent design properties to the decorative board on which the transparent resin film of the present invention is laminated. Such a decorative board comprising, in order in the thickness direction, a base material, a pattern layer, and the transparent resin film of the present invention is also one aspect of the present invention.

[0088] Next, a preferred example of the decorative board of the present invention will be described with reference to FIG. 3. In the decorative board 20 of the present invention, a pattern layer 24 is laminated on one surface of a base material 25, and the transparent resin film 10 of the present invention is laminated on the side opposite to the side of the pattern layer 24 having the base material 25. Further, from the viewpoint of making the adhesiveness between the pattern layer 24 and the transparent resin film 10 of the present invention stronger, it is preferable to have an adhesive layer 23. Hereinafter, each component of the decorative board of the present invention will be described.

[0089] (Base material) The above-mentioned base material is not particularly limited, and is appropriately determined according to the use of the decorative board using the transparent resin film of the present invention, for example.

[0090] The material constituting the above-mentioned base material is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, metal materials, and inorganic materials. Among them, as the material constituting the above-mentioned base material, a resin material or a wood material having rigidity and lightness is preferable. Also, these composite materials may be used. The above-mentioned resin material preferably contains a thermoplastic resin, for example. Examples of the thermoplastic resin include polyvinyl resins such as polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol resin; polyolefin resins such as polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene-(meth)acrylic acid resin; polyester resins such as polyethylene terephthalate resin (PET resin); acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, and single polymers and copolymers of thermoplastic resins such as polyvinyl chloride resin sheets; diene rubbers such as styrene-butadiene rubber, isoprene rubber, and chloroprene rubber; non-diene rubbers such as butyl rubber and ethylene-propylene rubber; natural rubber, thermoplastic elastomer, or a mixed resin thereof. Among them, polyolefin resins, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride resin, ionomer, etc. are preferable. Further, the above resin material may be foamed.

[0091] Thermoplastic resin sheets and thermosetting resin sheets may contain various additives such as colorants (pigments or dyes), fillers such as wood powder and calcium carbonate, matting agents such as silica, foaming agents, flame retardants, lubricants such as talc, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers, as required.

[0092] Examples of the above wood material include various materials such as cedar, cypress, oak, pine, lauan, teak, and merapi. Also, as the core material, any of veneers, wood veneers, plywood (including LVL), particle board, medium density fiberboard (MDF), high density fiberboard (HDF), glued laminated timber, etc. made from these materials, or a laminated material obtained by appropriately laminating these may be used. Examples of the above metal material include iron, aluminum, etc. Further, the above base material may contain an inorganic compound.

[0093] Also, the above base material may contain the aforementioned flame retardant. By containing the flame retardant, the flame retardancy of the above base material is further improved.

[0094] In addition, when the base material has a base material composed of a plurality of resins, the types of resins forming the base material composed of the plurality of resins may be the same or different, and the thicknesses of the base materials composed of the plurality of resins may be the same or different.

[0095] In the present invention, the base material may have a hollow structure, or a slit groove or a through hole may be provided in a part of the base material.

[0096] The thickness of the base material is not particularly limited. For example, it is preferably 0.01 mm or more, and more preferably 0.1 mm or more and 50 mm or less. Note that the base material includes substantially plate-like shapes other than flat plates, and those having unevenness or curved surfaces are also included.

[0097] (Pattern layer) The above base material has a pattern layer laminated on one side. The above pattern layer is a layer that imparts decorativeness to the decorative board of the present invention using the transparent resin film of the present invention. For example, it may be a concealed layer (solid printing layer) uniformly colored, or a pattern layer formed by printing various patterns using ink and a printing machine, or a layer combining the concealed layer and the pattern layer (hereinafter, a pattern layer).

[0098] By providing the above concealed layer, when the above-described base material is colored or has color unevenness, an intended color can be given to adjust the surface color. In addition, by providing the above pattern layer, a stone pattern imitating the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertine marble pattern), a fabric pattern imitating a cloth pattern or a cloth-like pattern, a tile pasting pattern, a brick stacking pattern, etc., or a combination of these such as a mosaic, patchwork, characters, symbols, abstract patterns, flower patterns, landscapes, characters, etc. can be imparted to the decorative sheet. These patterns are formed not only by multicolor printing using ordinary process colors of yellow, red, blue, and black, but also by multicolor printing by a special color method in which plates of individual colors constituting the pattern are prepared.

[0099] As the ink composition used for the above pattern layer, a composition obtained by appropriately mixing a binder resin with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, etc. is used. There is no particular limitation on the binder resin. For example, urethane resins, acrylic resins, urethane-acrylic resins, urethane-acrylic copolymer resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, acrylic resins, polyester resins, nitrocellulose resins, etc. are preferably mentioned. As the above binder resin, any one of these can be used alone or in combination of two or more. Moreover, as the above colorant, inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, lead yellow, titanium yellow, valve pattern, cadmium red, ultramarine blue, cobalt blue, etc., organic pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, etc., or dyes, metallic pigments composed of flaky foil pieces such as aluminum and brass, and pearl gloss (pearl) pigments composed of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate are preferably mentioned.

[0100] The thickness of the above pattern layer is not particularly limited. For example, 0.1 μm or more is preferable, and 0.5 μm or more and 600 μm or less is more preferable. If the thickness of the above pattern layer is within the above range, an excellent design can be imparted to the decorative board of the present invention, and concealability can also be imparted. In addition, when the above base material itself has design properties in advance, such as a veneer, the pattern layer may not be provided.

[0101] The thickness of the decorative board of the present invention is not particularly limited. For example, 0.05 mm or more is preferable, and 1 mm or more and 50 mm or less is more preferable.

[0102] (Adhesive layer) The decorative board of the present invention preferably has an adhesive layer between the above pattern layer and the transparent resin film of the present invention. The above adhesive layer is a layer provided between the above pattern layer and the base sheet of the transparent resin film of the present invention. By having the adhesive layer, the adhesiveness between the pattern layer and the transparent resin film of the present invention can be made stronger.

[0103] It is preferable that the above adhesive layer contains a binder resin. As the binder resin contained in the above adhesive layer, the binder resin used in the above-described primer layer for adhesion can be preferably used. Also, the method of attaching the above adhesive layer is not particularly limited. For example, it can be obtained by laminating using a heat melting method, a thermal lamination method, and in addition to water-based adhesives, heat-sensitive adhesives, pressure-sensitive adhesives, hot melt adhesives, etc.

[0104] (Method for manufacturing a decorative board) Examples of the method for manufacturing the decorative board of the present invention include a method of laminating the above base material, the above pattern layer, and the above transparent resin film using an adhesive or the like for forming the above adhesive layer described above. Among them, it is preferable that the method for manufacturing the above decorative board includes a step of forming an adhesive layer on the surface of the above transparent resin film on the side to be laminated with the above pattern layer, and a step of bonding the above transparent resin film and the above pattern layer via the above adhesive layer. The method for manufacturing such a decorative board of the present invention is also an aspect of the present invention. In the above transparent resin film, when forming an uneven shape on the surface protection layer side, embossing or the like is performed to form an uneven shape. However, following the uneven shape on the side where the embossing is performed, a slight uneven shape is also formed on the surface opposite to the side where the embossing is performed (the side to be laminated with the pattern layer). In such a case, so-called air gami may occur, where air enters the uneven shape on the side of the transparent resin film to be laminated with the above pattern layer, and the design property may be reduced. In the method for manufacturing the decorative board of the present invention, since it has a step of forming an adhesive layer on the surface of the transparent resin film on the side where the pattern layer is laminated, the adhesive layer can also enter the concave portions of the uneven shape on the side where the pattern layer is laminated, preventing the generation of the above-described air bubbles and suppressing the deterioration of the design property.

Example

[0105] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

[0106] (Example 1) A transparent polypropylene film (thickness: 60 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adeka Stab LA-46, manufactured by ADEKA Corporation) was prepared, and an adhesive primer agent, which is a two-component reactive urethane resin using isocyanate as a curing agent, was applied to one surface of the transparent polypropylene film to provide an adhesive primer layer with a thickness of 2 μm. Next, a flame retardant (phosphinic acid metal salt-based flame retardant, product name: Pekoflam STC, manufactured by Archroma) containing transparent polypropylene-based resin (thickness: 80 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adeka Stab LA-46, manufactured by ADEKA Corporation) was melt-extruded onto the other surface of the transparent polypropylene film (the surface opposite to the adhesive primer layer), and they were laminated by a thermal lamination method to obtain a two-layer transparent resin layer. The content of the above flame retardant was 6 parts by mass of the phosphinic acid metal salt-based flame retardant with the mass of the flame retardant-containing transparent polypropylene-based resin being 100 parts by mass. The thickness of the two-layer transparent resin layer was 140 μm, and the content of the phosphinic acid metal salt-based flame retardant was 3.3% by mass with the total mass of the two-layer transparent resin layer being 100% by mass. After the surface of the above flame retardant-containing transparent polypropylene-based resin was subjected to corona treatment, a primer layer, which is a two-component reactive urethane resin using isocyanate as a curing agent, was applied to a thickness of 2 μm. On the surface of the primer layer, urethane (meth) acrylate, which is a radiation-curing resin containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adeka Stab LA-46, manufactured by ADEKA Corporation), was coated by a gravure coating method to a thickness of 15 μm, and then irradiated with an electron beam under the conditions of an acceleration voltage of 165 keV and 5 Mrad to form a surface protection layer. After heating the surface protection layer side with an infrared non-contact heater, immediately embossing was performed by hot pressing to impart an uneven shape, and a transparent resin film was produced. The obtained transparent resin film had a total thickness of 159 μm, and the thickness of the concave portion of the uneven shape was 105 μm. On the other hand, HDF (high-density fiberboard) (thickness: 3 mm) was prepared, and a pattern layer was provided on one surface of the HDF to a thickness of 2 μm by an inkjet printer to prepare a substrate. A two-component curable polyester resin (thickness: 30 μm) using isocyanate as a curing agent was applied to the adhesive primer layer side of the obtained transparent resin film, and the transparent resin film was laminated so that the adhesive primer layer side and the surface provided with the pattern layer side of the substrate were in contact with each other to produce a decorative panel. Then, a pressure of 10 kg / m 2 was applied and the product was cured for 3 days at room temperature in an ambient environment.

[0107] (Example 2) A transparent resin film and a decorative panel were produced in the same manner as in Example 1, except that the flame retardant contained in the flame retardant-containing transparent polypropylene-based resin was changed to a phosphazene-based flame retardant (phosphazene-based flame retardant, Labitol FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.). The content of the phosphazene-based flame retardant was 3.1% by mass based on the total mass of the two-layer transparent resin layer being 100% by mass.

[0108] (Example 3) As the transparent polypropylene-based resin for melt extrusion, a transparent polypropylene-based resin (thickness 30 μm, transparent resin layer) containing a flame retardant (phosphazene-based flame retardant, Rabitol FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.) and hydrophilic fumed silica (AEROSIL 50 manufactured by Nippon Aerosil Co., Ltd.) was used, and a transparent resin film was produced in the same manner as in Example 2 except for this, and a decorative material was produced in the same manner as in Example 1. The contents of the above-mentioned flame retardant and hydrophilic fumed silica were each 6 parts by mass based on 100 parts by mass of the mass of the flame retardant-containing transparent polypropylene-based resin. The thickness of the two-layer transparent resin layer was 140 μm, and the contents of the flame retardant and hydrophilic fumed silica were each 3.1% by mass based on 100% by mass of the total mass of the two-layer transparent resin layer.

[0109] (Comparative Example 1) A transparent resin film and a decorative board were produced in the same manner as in Example 1 except that the transparent polypropylene-based resin for melt extrusion did not contain a flame retardant.

[0110] (Comparative Example 2) A transparent polypropylene film (thickness 60 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adeka Stab LA-46, manufactured by ADEKA Corporation) and a flame retardant-containing transparent polypropylene-based resin (thickness 60 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adeka Stab LA-46, manufactured by ADEKA Corporation) were used, and a transparent resin film and a decorative board were produced in the same manner as in Example 1 except that the concave part of the uneven shape of the transparent resin film was made 90 μm by the uneven shape.

[0111] (Example 4) A transparent resin film and a decorative board were produced in the same manner as in Example 1 except that the thickness of the primer for adhesion was 13 μm.

[0112] (Example 5) A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that 3 parts by mass of a silver phosphate glass-supported compound (manufactured by Koa Glass Co., Ltd. / PG-711) was added as an antiviral agent to 100 parts by weight of the radiation-curable resin.

[0113] (Example 6) A transparent resin film and a decorative board were produced in the same manner as in Example 1, except that an anionic phenolic material (EXP20530A manufactured by DIC Corporation) having anti-allergenic properties was blended at a solid content ratio of 23% by mass, and a zinc-based material (EXP20530B manufactured by DIC Corporation) having anti-allergenic properties was blended at a solid content ratio of 23% by mass with respect to the radiation-curable resin.

[0114] (Evaluation method) <Design property> Regarding the decorative boards obtained in the examples and comparative examples, the printed patterns were visually confirmed and evaluated according to the following criteria. The results are shown in Table 1. ++: The printed pattern is clearly visible. +: The printed pattern is slightly cloudy. -: The printed pattern is not clearly visible.

[0115] <Color difference after weather resistance test> The decorative boards obtained in the examples and comparative examples were put into an accelerated weather resistance tester (Eye Super UV Tester manufactured by Iwasaki Electric Co., Ltd.) set under the following conditions, and irradiated for 20 hours and dew-condensed for 4 hours as one cycle, and after 17 cycles of operation, they were taken out. (Accelerated test conditions) · Black panel temperature: 63°C · Humidity: 50%RH · Irradiation intensity: 60W / m 2 (365nm) Thereafter, the color difference change of the decorative sheet before and after the above accelerated test was measured with a color difference meter (CR-300 manufactured by Minolta Co., Ltd.). That is, the L value, a value, and b value of the decorative sheet before and after the accelerated test were measured, and the color difference change ΔE was calculated by the following formula 1 and evaluated according to the following criteria. The results are shown in Table 1. ΔE = [(ΔL) 2 +(Δa) 2 +(Δb)2 1 / 2 Formula 1 ++: ΔE < 1.0 +: 1.0 ≤ ΔE < 1.5 -: ΔE ≥ 1.5 ΔL = |L value (after weathering test) - L value (before weathering test)| Δa = |a value (after weathering test) - a value (before weathering test)| Δb = |a value (after weathering test) - a value (before weathering test)|

[0116] <Abrasion resistance (Taber abrasion test)> For the decorative panels obtained in the examples and comparative examples, in accordance with the Japanese Agricultural and Forestry Standards for flooring; Abrasion A test, using a Taber-type abrasion tester (manufactured by Rigaku Kogyo Co., Ltd.) and abrasion paper (S-42), a test was conducted at a load of 1 kg, and the remaining pattern of the pattern layer after 1500 rotations was evaluated. The results are shown in Table 1. +: More than half of the pattern layer remains -: Less than half of the pattern layer remains

[0117] <Flammability evaluation> [Horizontal flammability (Flammability: Difficulty of fire spread)] The decorative panel was cut into a size of 9 cm × 30 cm to obtain a test piece. As shown in FIGS. 4(a) and (b), a rectangular metal base 103 was placed on the base 102 of a commercially available household heater 101 (voltage AC100V, power consumption 1200W), and the test piece 105 was placed in a metal frame 104 installed on the base. A test on the difficulty of fire spread was conducted with the heater at a 45° angle and the heater output adjusted to 4 / 5 of the output. Specifically, the test piece was preheated for 2 minutes using the above household heater. Then, as shown in FIG. 4(a), the end 106 of the test piece on the heater side in the longitudinal direction was heated with a lighter 107 for 1 minute to ignite, and then the test piece 105 was allowed to burn longitudinally as shown in FIG. 4(b). Then, the burning state was visually observed, and the burning distance (L1) was evaluated as follows. The results are shown in Table 1. [Burning distance (L1)] ​The test piece was ignited, the flame of the lighter was removed, and the spread distance of the flame from the initial ignition was measured as the spread distance (L1), and the evaluation was carried out according to the following evaluation criteria. If it is + evaluation or higher, it is evaluated that there is no problem in actual use. +: L1 is less than 10 cm -: L1 is 10 cm or more

[0118] <Antiviral property> For the transparent resin films prepared in Example 1 and Example 5, an antiviral performance test was carried out by a method compliant with the antiviral test method (ISO21702), and the antiviral activity value against influenza virus was evaluated. The results are shown in Table 3. +: Antiviral activity value of 2.0 or more -: Antiviral activity value less than 2.0

[0119] <Anti-allergenic property> The transparent resin films prepared in Example 1 and Example 6 were cut into small pieces, and the amount of allergen after being immersed in a mite allergen aqueous solution for 1 day was visually confirmed by horizontal development chromatography (Mighty Checker). The results are shown in Table 4. +: A decrease in the amount of allergen was confirmed -: A decrease in the amount of allergen was not confirmed

[0120]

Table 1

[0121]

Table 2

[0122]

Table 3

[0123]

Table 4

[0124]

Table 5

[0125] In the decorative board according to the embodiment, it was confirmed that it has excellent design properties and is also excellent in weather resistance and flame retardancy. Further, from Example 3, it was confirmed that the design properties are improved by the thermoplastic resin layer containing a flame retardant and a filler, and from Example 1, it was confirmed that the design properties are improved by having an adhesive primer layer with a predetermined thickness. On the other hand, in Comparative Example 1 using a transparent resin film not containing a flame retardant, it was inferior in flame retardancy, and in Comparative Example 2 where the thickness of the concave portion of the uneven shape was less than 100 μm, it was inferior in weather resistance and abrasion resistance. From Table 4, it was confirmed that the transparent resin film produced in Example 5 has antiviral properties. From Table 5, it was confirmed that the transparent resin film produced in Example 6 has anti-allergenic properties.

Industrial Applicability

[0126] According to the present invention, it is possible to impart excellent design properties to a decorative board and provide a transparent resin film that is also excellent in weather resistance and flame retardancy. The decorative board of the present invention has excellent design properties and excellent weather resistance, so it is suitably used for interior building materials such as furniture, doors such as sliding doors, floor coverings, walls, ceilings, and various decorative molded bodies.

Explanation of Signs

[0127] 10 Transparent resin film 11 Surface protection layer 12 Transparent resin layer 13 Adhesive primer layer 20 Decorative board 23 Adhesive layer 24 Pattern layer 25 Base material 101 Household heater 102 Stand for household heater 103 Rectangular base 104 Metal frame 105 Test piece 106 End part 107 Lighter

Claims

1. A transparent resin film for protecting a pattern layer laminated on one side of a base material, wherein the transparent resin film has at least a surface protection layer and a transparent resin layer laminated thereon, has an uneven shape on the surface protection layer side, the thickness of the concave portion of the uneven shape of the transparent resin film is 100 μm or more, the transparent resin film contains an ultraviolet absorber and a flame retardant, and the flame retardant is a metal phosphinate-based flame retardant characterized in that it is a transparent resin film.

2. The transparent resin film according to claim 1, wherein the ultraviolet absorber is contained in the surface protection layer and / or the transparent resin layer.

3. The transparent resin film according to claim 1 or 2, which has an adhesive primer layer on the side opposite to the surface protection layer side of the transparent resin layer.

4. The transparent resin film according to claim 3, wherein the adhesive primer layer has a thickness of 0.5 μm or more and 10 μm or less.

5. The transparent resin film according to claim 1, 2, 3, or 4, wherein the ultraviolet absorber is a triazine-based ultraviolet absorber.

6. The transparent resin film according to any one of claims 1 to 5, wherein the transparent resin layer contains a flame retardant.

7. The transparent resin film according to any one of claims 1 to 6, wherein the surface protection layer contains a flame retardant.

8. The transparent resin film according to any one of claims 1 to 7, wherein the surface protection layer contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent.

9. The transparent resin film according to any one of claims 1 to 8, wherein the transparent resin layer contains a filler.

10. A decorative panel characterized by comprising, in the thickness direction, in order, a base material, a pattern layer, and the transparent resin film according to any one of claims 1 to 9.

11. The decorative panel according to claim 10, which has an adhesive layer between the pattern layer laminated on one side of the base material and the transparent resin film.

12. A method for manufacturing the decorative panel according to claim 10 or 11, comprising a step of forming an adhesive layer on the surface of the transparent resin film on the side to be laminated on the pattern layer, and a step of bonding the transparent resin film and the pattern layer through the adhesive layer characterized in that it is a method for manufacturing a decorative panel.

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