JP2021151777A - Transparent resin film, decorative sheet and manufacturing method of decorative sheet - Google Patents

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

The present invention relates to a transparent resin film, a decorative plate made of the transparent resin film, and a method for producing the decorative plate.

In recent years, with the spread of the inkjet printing method using an inkjet printer, it is possible to handle a wide variety of small lots of decorative sheets used for building materials and decorative molded products, and complicated patterns (characters, characters, as a pattern layer). It has become possible to print numbers and figures).
Further, the inkjet printing method has an advantage that the base material to be printed is not limited to a film, but can be printed on a flat plate, a base material having irregularities or curved surfaces.
However, since the pattern layer printed by the inkjet printing method is usually on the outermost surface of the base material, the surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient, and the pattern layer is protected. It was necessary to laminate a transparent resin film on the surface of the pattern layer.
As such a transparent resin film, for example, in Patent Document 1, 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. Overlaminated films are disclosed.

However, in the conventional transparent resin film, although the designability is improved by having the uneven shape, the weather resistance varies due to the difference in thickness due to the uneven shape, and the weather resistance is particularly inferior in the thin film portion. There was room for improvement.
In particular, a wide variety of inks are used for the pattern layer printed by the inkjet printing method, and this tendency is remarkable.

Further, 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 satisfy the requirement for obtaining non-combustibility certification, which indicates that it is hard to burn in the event of a fire. Here, the above requirements for obtaining non-combustibility certification are the total calorific value, maximum calorific value, cracks, and heat generation test in accordance with ISO5660-1 specified in Article 2, Item 9 of the Building Standards Act of Japan. It is a predetermined requirement for the generation of holes.

As a decorative sheet used for a decorative board that meets the above requirements, a base sheet, a transparent resin layer, and a surface protective layer are laminated in this order, the thickness of each layer is in a specific range, and a flame retardant is contained. A decorative sheet to be used has been proposed (see, for example, Patent Document 2).

The above-mentioned decorative sheet is also a decorative sheet having excellent nonflammability, but it has not been studied that the decorative sheet on the base material does not easily burn and spread in the event of a fire. For members that are installed on a horizontal surface such as floor decorative materials, the expansion of the area of the decorative sheet that is burning in the event of a fire is suppressed, the fire does not spread easily, and it is also flame-retardant in order to secure evacuation time. It is an important performance.

Therefore, it is desired to develop a transparent resin film having excellent weather resistance, which is difficult to spread even in a thin film portion, and which is excellent in flame retardancy.

Japanese Unexamined Patent Publication No. 2005-120255 Japanese Unexamined Patent Publication No. 2015-182379

According to the present invention, even if a concave-convex shape is formed on the surface in order to impart excellent designability, excellent weather resistance can be obtained even in the concave-convex shape of the transparent resin film, and flame retardancy is further improved. It is an object of the present invention to provide a transparent resin film having a transparent resin film, a decorative plate made of the transparent resin film, and a method for producing the decorative plate.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have a concavo-convex shape on the opposite side surface of the transparent resin film on the side to be laminated on the pattern layer, and the transparent shape formed by the concavo-convex shape. The concave-convex concave portion of the sex resin film has a predetermined thickness, and the transparent resin film contains an ultraviolet absorber and a flame retardant, so that the surface of the transparent resin film can be given excellent design. It has been found that a transparent resin film having excellent weather resistance and flame retardancy can be obtained even if an uneven shape is formed on the surface, and the present invention has been completed.

The present invention is a transparent resin film for protecting a pattern layer laminated on one of the base materials, and the transparent resin film is obtained by laminating at least a surface protective layer and a transparent resin layer. The surface protective layer has a concavo-convex shape, the thickness of the concavo-convex concave portion of the transparent resin film is 100 μm or more, and the transparent resin film contains an ultraviolet absorber and a flame retardant. It is a transparent resin film.

In the transparent resin film of the present invention, the ultraviolet absorber is preferably contained in the surface protective 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 protective layer side of the transparent resin layer.
The thickness of the adhesive primer layer is preferably 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 antiallergen agent.
Further, the flame retardant is preferably at least one selected from the group consisting of a phosphinic acid metal salt-based flame retardant, a phosphazene-based flame retardant, and a NOR-type hindered amine-based flame retardant.
Further, the transparent resin layer preferably contains a filler.

The present invention is also a decorative board, which comprises, in order in the thickness direction, a base material, a pattern layer, and the transparent resin film of the present invention.

The decorative board of the present invention preferably has an adhesive layer between the pattern layer laminated on one of the base materials and the transparent resin film.
The present invention is the method for producing a decorative board of the present invention, wherein an adhesive layer is formed on the surface of the transparent resin film on the side to be laminated on the pattern layer, and the above is performed through the adhesive layer. It is also a method for manufacturing a decorative board, which comprises a step of laminating a transparent resin film and the above-mentioned pattern layer.

The present invention can impart excellent designability to a decorative board, and can provide a transparent resin film having excellent weather resistance and flame retardancy.
The decorative board of the present invention made of such a transparent resin film of the present invention has excellent design properties, and is also excellent in weather resistance and flame retardancy.

It is a schematic diagram which shows the cross section of an example of the transparent resin film of this invention. It is a schematic diagram which shows the cross section of a preferable example of the transparent resin film of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative board of this invention. 4 (a) and 4 (b) are schematic views for explaining a method for evaluating flame retardancy.

<Transparent resin film>
First, the transparent resin film of the present invention will be described.
In the transparent resin film of the present invention, at least a surface protective layer and a transparent resin layer are laminated, and the surface protective layer side has a concave-convex shape, and the thickness of the concave-convex concave portion is equal to or larger than a predetermined value. Moreover, the transparent resin film contains an ultraviolet absorber and a flame retardant.
In the conventional transparent resin film, the uneven shape causes a difference in thickness, and the amount of the ultraviolet absorber is reduced in the portion where the film thickness is thin (concave concave portion of the concave-convex shape), and sufficient weather resistance is obtained. I couldn't.
However, in the transparent resin film of the present invention, the thickness of the concave-convex-shaped recess is sufficiently secured, and the concave-convex-shaped recess also contains the ultraviolet absorber, so that the thin film portion generated by the concave-convex shape is also sufficient. Since weather resistance can be obtained and a flame retardant is contained, excellent flame retardancy can be obtained.
In addition, in this specification, "the ultraviolet absorber is also contained in the concave-convex-shaped concave portion" means that the bottom of the concave-convex-shaped concave portion of the transparent resin film of the present invention and the transparent resin film in cross-sectional view. It means that an ultraviolet absorber is present between the surface protective layer and the opposite side surface. Specifically, on the surface of the transparent resin film of the present invention on the surface protective layer side, a 10 cm ² region including a concave-convex concave portion is cut out to prepare a sample, and the sample prepared using a freeze-crusher is finely divided. By crushing, extracting the ultraviolet absorber with THF (tetrahydrofuran), diluting with methanol, acetone, IPA, etc., and then measuring with a liquid chromatograph, the ultraviolet absorber can be found even in the concave and convex recesses. It is possible to determine whether or not it is included.

A preferred example of the transparent resin film of the present invention will be described with reference to FIG.
As shown in FIG. 1, the transparent resin film 10 of the present invention has a transparent resin layer 12, a surface protective layer 11 on one surface thereof, and 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 the design property is deteriorated due to scratches. Can be suitably prevented.
Further, as shown in FIG. 2, the transparent resin film 10 of the present invention preferably has an adhesive primer layer 13 on the side surface of the transparent resin layer 12 opposite to the surface protective layer 11 side.
The transparent resin film 10 of the present invention has a primer (from the viewpoint of further strengthening the adhesiveness between the transparent resin layer 12 and the surface protective layer 11 between the transparent resin layer 12 and the surface protective layer 11. (Not shown) is preferable.
Hereinafter, each configuration of the transparent resin film of the present invention will be described.

(Transparent resin layer)
The transparent resin layer is a layer that plays a role of protecting the pattern layer laminated on one surface of the base material described later. The transparent resin layer may be translucent or colored as long as the pattern layer described later is visible as long as it is transparent.
The transparent resin layer contains one or more of the following resins, and is preferably made of a thermoplastic resin. Examples of the thermoplastic resin include polyethylene, polypropylene, polybutene, polymethylpentene, and olefin heat. Olefin resins such as plastic elastomers, polyethylene terephthalates, polybutylene terephthalates, polyethylene narefurates, ethylene glycol-terephthalic acid-isophthalic acid copolymers, terephthalic acid-ethylene glycol-1,4 cyclohexanedimethanol copolymers, polyester-based thermoplastics Polyester resin such as elastomer, polymethyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, acrylic resin such as methyl (meth) acrylate-styrene copolymer, polycarbonate resin, polyvinyl chloride, polystyrene , Ionomer, etc. Among them, polypropylene is preferably used because it has high tensile strength, excellent chemical resistance, and excellent production process.
In addition, in this specification, (meth) acrylate means acrylate or methacrylate.

The transparent resin layer may be unstretched, but may be uniaxially stretched or biaxially stretched as necessary.
The thickness of the 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 transparent resin layer is less than 20 μm, the tensile strength may be insufficient and the surface of the pattern layer may not be protected. If it exceeds 500 μm, the transmittance of the transparent resin film of the present invention decreases. The visibility of the pattern in the pattern layer may be reduced.

The transparent resin layer may be composed of one layer or a laminated body composed of two or more layers.

Further, when the transparent resin layer is a laminate composed of a plurality of layers, the types of resins constituting the layer to be formed may be the same or different, and the layer composed of a plurality of resins may be used. The thickness may be the same or different.
The method of laminating the transparent resin layer in two or more layers is not limited to a general method, and examples thereof include a dry laminating method and an extrusion heat laminating method.

The transparent resin layer preferably contains a flame retardant.
When the transparent resin layer is composed of a plurality of layers, it is effective to improve the flame retardancy if the layer closer to the surface protective layer contains a flame retardant.

The flame retardants include phosphinic acid metal salt flame retardants, phosphazen flame retardants, NOR type hindered amine flame retardants, halogen flame retardants, antimon flame retardants, metal hydroxide flame retardants, and phosphoric acid ester flame retardants. And so on.
Among them, selected from the group consisting of phosphinic acid metal salt-based flame retardants, phosphazen-based flame retardants, and NOR-type hindered amine-based flame retardants from the viewpoint of the environment or the point that the amount of addition can be suppressed and the transparency of the layer containing the flame retardant can be maintained. It is preferable that it is at least one kind, which has a property of trapping radicals generated from organic substances during combustion and making it difficult to continue combustion, and in a horizontal combustibility test, a metal phosphinic acid salt in terms of the effect of suppressing the spread of combustion. NOR type hindered amine flame retardants are preferably contained at least one selected from the group consisting of flame retardants and phosphazen flame retardants, and have the effect of reducing the calorific value in the heat generation test of ISO5660-1. preferable.

Examples of the phosphinic acid metal salt-based flame retardant include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphine, zinc bisdiphenylphosphinate, zinc bismethylethylphosphine, and zinc bisdiphenylphosphine. , Titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate.
Commercially available products of the above phosphinic acid metal salt flame retardant include Clariant Japan's product names "EXOLITE OP-930", "EXOLITE OP-935", "EXOLITE OP-1230", "EXOLITE OP-1240", and "EXOLITE". OP-1312 ”and the like.

Examples of the phosphazene-based flame retardant include phenoxyphosphazene and (poly) tolyloxyphosphazene (eg, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, _{Cyclic and / or chain C 1-6} alkyl C _6-20 such as p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xsilyloxyphosphazene, etc. Aryloxyphosphazene and (poly) phenoxytriloxyphosphazene (eg, phenoxyo-tolyloxyphosphazene, phenoxym-tolyloxyphosphazene, phenoxyp-tolyloxyphosphazene, phenoxyo, m-tolyloxyphosphazene, phenoxyo, p- Circular and / Alternatively, chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxyphosphazene and the like can be exemplified, preferably cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _{6-. 20} aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or chain triloxyphosphazene, cyclic and / or chain phenoxytrilphenoxyphosphazene, etc.) Be done.
Further, a compound having a cross-linked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), a compound having a cross-linked structure of 2,2- (4,4'-diphenylene) isopropyrine group, 4,4'-. Examples thereof include compounds having a cross-linked structure of 4,4'-diphenylene groups, compounds having a cross-linked structure of oxydiphenylene groups, compounds having a cross-linked structure of 4,4'-thiodiphenylene groups, and the like.

Examples of the NOR-type hindered amine-based flame retardant include 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecilaminopiperidin; bis (1-octyloxy-2,2,6,6-tetra). Methylpiperidin-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; 4,4'-Hexamethylenebis (Amino-2,2,6,6-Tetra) Methylpiperidin) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6--) end-capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine. Tetramethylpiperidin-4-yl) butylamino] -s-Triazine and an oligomeric compound; 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) , 2-Chloro-4,6-bis (dibutylamino) -s-triazine-terminated 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-) 4-yl) Butyamino] -an oligomeric compound that is a condensing product with s-triazine; 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)- 6-Chloro-s-triazine; peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, N, N' -Reaction product with ethane-1,2-diylbis (1,3-propanediamine) (N, N', N'''-tris {2,4-bis [(1-cyclohexyloxy-2,2,2) 6,6-Tetramethylpiperidin-4-yl) n-butylamino] -s-triazine-6-yl} -3,3'-ethylenediiminodipropylamine); bis (1-undecanoxy-2,2,2) 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 can be mentioned. Examples of commercially available NOR-type hindered amine flame retardants include Flamestab NOR116FF manufactured by BASF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, TINUVIN PA123, and LA-81 manufactured by ADEKA CORPORATION.

The flame retardant may be used alone or in combination of two or more.

The content of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, with the total mass of the transparent resin layers as 100% by mass. The content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less, with the total mass of the transparent resin layers as 100% by mass. When the lower limit of the content of the flame retardant is in the above range, the flame retardancy of the transparent resin film is further improved. Further, when the upper limit of the content of the flame retardant is within the above range, the transparency of the transparent resin film is further maintained.

At least one layer of the transparent resin layer may contain a filler. The filler is not particularly limited as long as the transparency of the transparent resin layer is not impaired, and the sharpness of the decorative board using the transparent resin film (meaning the visibility of the pattern layer described later) is further improved. In terms of points, a filler showing an average particle size equal to or less than the wavelength of visible light is preferable. Examples of the filler include inorganic fillers such as silica, calcium carbonate, talc, and clay.

The filler is preferably contained in at least one of the transparent resin layers, and is preferably contained in the same layer as the layer containing the flame retardant. That is, it is preferable that at least one of the transparent resin layers contains a flame retardant and a filler.

When at least one of the transparent resin layers contains a flame retardant, the transparent resin layer preferably further contains an inorganic filler having a polar group on the surface. Since the transparent resin layer containing the flame retardant contains 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. do. It is considered that this is because the polar portion 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, and examples thereof include an inorganic filler having a hydroxyl group such as a silanol group on the surface, and more specifically, hydrophilic silica is used. Can be done.

The silica used as the filler may be either a natural product or a synthetic product, and may be either crystalline or amorphous. Further, the synthetic amorphous silica may be prepared by either a wet method or a dry method. The synthetic wet method silica prepared by the wet method is not particularly limited, and examples thereof include a sedimentation method and a gel method. Synthetic dry method prepared by the dry method The method for preparing silica is not particularly limited, and examples thereof include a combustion method and an arc method. As the silica, silica having a small average particle size is preferable from the viewpoint of further improving the sharpness of the decorative board using the transparent resin film, and fumed silica and hydrophilic fumed silica obtained by a combustion method are more preferable.

The BET specific surface area of the filler such as hydrophilic fumed silica ^{is preferably 50 m 2} / g or more, more preferably 130 m ² / g or more, and further preferably ^{200 m 2 / g or more.} Since the lower limit of the BET specific surface area of the filler is within the above range, the average particle size is small and the amount of silanol increases in the case of hydrophilic fumed silica. Therefore, the transparent resin layer is made transparent by adding the filler. The decrease in property is further suppressed, the dispersibility of the flame retardant is further improved, 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 the content of the flame retardant can be reduced.

In the present specification, the BET specific surface area is the BET specific surface area measured by the nitrogen adsorption method by the measuring method based on DIN66131.

As the hydrophilic fumed silica used as the filler, a commercially available product can be used. Examples of such commercially available products include AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, and AEROSIL 380 manufactured by Japan Aerosil Co., Ltd.

When the transparent resin layer contains a flame retardant and a filler, the content of the filler in the transparent resin layer is 50 parts by mass or more, with the content of the flame retardant in the transparent fat layer being 100 parts by mass. Is preferable, 100 parts by mass or more is more preferable, and 200 parts by mass or more is further preferable. 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. 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 further preferably 10 parts by mass or less.

The 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 deviating from the gist of the present invention. ..
Further, the transparent resin layer has a matting agent, a foaming agent, a lubricant, an antistatic agent, an antioxidant, a light stabilizer, a radical scavenger, etc. so as to further improve performance such as heat resistance and shrinkage. Various additives such as soft components (eg, rubber) may be included.

(Surface protective layer)
By having the above surface protective layer, the durability (scratch resistance, stain resistance, weather resistance, etc.) of the transparent resin film of the present invention becomes more excellent, and the surface of the pattern layer can be more preferably protected. , The deterioration of the design due to the scratching of the transparent resin film itself of the present invention can be suitably prevented.
The surface protective layer may have a single layer structure, a plurality of layer structures made of the same or different materials, or the materials shown below may be appropriately mixed.

The surface protective layer is not particularly limited, and examples thereof include those made of a crosslinked cured product of a two-component curable resin and an ionization radiation curable resin composition, and the crosslinked cured product is preferably transparent and transparent. As long as the pattern layer described later is visible, it may be translucent or colored.
As the two-component curable resin, a binder resin for an adhesive primer layer, which will be described later, may be used.
Examples of the ionizing radiation curable resin composition include oligomers having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule (hereinafter, so-called prepolymers, macromonomers and the like are also included) and / or in the molecule. A monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle having an energy capable of polymerizing or cross-linking a molecule, and usually, an electron beam (EB) or an ultraviolet ray (UV) is generally used.

Examples of the oligomer or monomer include compounds having a radically polymerizable unsaturated group such as a (meth) acryloyl group, 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 admixture of a plurality of types. In addition, in this specification, the said (meth) acryloyl group means an acryloyl group or a methacryloyl group.

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. Can be preferably used, and urethane (meth) acrylate oligomers are more preferable. As the molecular weight, a molecular weight of about 2.5 to 100,000 is usually used.

Further, 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, and trimethylolpropane. Ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate {5-functional (meth) acrylate}, dipentaerythritol hexa (meth) acrylate {six-functional (meth) acrylate} And so on. Here, the polyfunctional monomer means a monomer having a plurality of radically polymerizable unsaturated groups.

In the present invention, it is more preferable that the above-mentioned ionized radiation curable resin composition contains an ionized radiation curable resin component composed of a urethane acrylate oligomer and a polyfunctional monomer, and the ionized radiation curable resin component includes a urethane acrylate oligomer / polyfunctional monomer. It is particularly preferable that the monomer (mass ratio) is 6/4 to 9/1. Within this mass ratio range, scratch resistance can be made more excellent.
If necessary, in addition to the ionizing 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, and phenoxyethyl (meth) acrylate.

When the ionizing radiation curable resin composition is crosslinked with ultraviolet rays, it is preferable to add a photopolymerization initiator to the ionizing radiation curable resin composition.
When the ionizing radiation curable resin composition is a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoins, and benzoin methyl ethers are used alone or in combination as the photopolymerization initiator. Can be used.
When the ionizing radiation curable resin composition is a resin system having a cationically polymerizable unsaturated group, the photopolymerization initiator includes an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, and a benzoin. Sulfonic acid esters and the like can be used alone or as a mixture. The amount of these photopolymerization initiators added is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin component.

If necessary, various additives may be further added to the ionizing radiation curable resin composition. Examples of these additives include 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, and acrylic resin. , Thermoplastic resins such as cellulose resins, lubricants such as silicone resins, waxes and fluororesins, UV absorbers such as benzotriazole, benzophenone and triazine, light stabilizers such as hindered amine radical traps, silica, acrylic beads, mica Etc., a colorant such as a luster, a tactile sensation adjuster, a dye, and a pigment.

The above-mentioned flame retardant may be added to the surface protective layer.
As the flame retardant, those described in the transparent resin layer can be appropriately selected and used, and are selected from the group consisting of phosphinic acid metal salt-based flame retardants, phosphazene-based flame retardants and NOR-type hindered amine-based flame retardants. At least one type is preferable, and a NOR type hindered amine flame retardant is more preferable. By adding a flame retardant to the surface protective layer, char flammability can be reduced because char formation, radical scavenging ability in combustion gas, and the like are exhibited against heat applied from the surface during combustion.
Regarding the content of the flame retardant in the surface protective layer, the lower limit of the content of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, assuming that the total mass of the surface protective layer is 100% by mass. The upper limit of the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less.

Further, the surface protective layer contains the flame retardant and the inorganic filler 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. Is preferable.
As the inorganic filler, those described in the transparent resin layer can be appropriately selected and used, and silica is preferable, and fumed silica is more preferable in consideration of the dispersibility of the flame retardant, and the fumed silica is more preferable. Among the silicas, hydrophilic fumed silica is more preferable.

The surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent. When the surface protective layer contains an antibacterial agent and an antiviral agent, the transparent resin film can be imparted with antibacterial and antiviral properties.
Further, when the sex surface protective layer contains an anti-allergen agent, the transparent resin film can be imparted with anti-allergen properties.

The antibacterial agents and antiviral agents can be generally classified into organic and inorganic agents.
Examples of organic antibacterial agents and antiviral agents 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. be.
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.

Among the above organic antibacterial agents and antiviral agents, benzimidazole compounds or anionic compounds that maintain the particle shape are preferably used.
The above-mentioned "maintaining the particle shape" means that it exists in the state of particles without being dissolved in the ionizing radiation curable resin composition which is the curable resin of the surface protective layer. Therefore, in the process of forming the surface protective layer, the particles of the benzimidazole compound or the particles of the anionic compound are likely to emerge, and the particles of the benzimidazole compound or the anionic compound are on the outermost surface side of the surface protective layer. Particles can be easily unevenly distributed.
Then, by unevenly distributing the particles of the benzimidazole compound or the particles of the anionic compound on the outermost surface side of the surface protective layer, an antibacterial agent or an antiviral agent necessary for obtaining predetermined antibacterial and antiviral properties. Since the amount of the virus added can be suppressed, it is possible to easily suppress the deterioration of the scratch resistance of the surface protective layer.

As the anionic antibacterial agent and antiviral agent, for example, those containing 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 of the structures of styrene, Na sulfonic acid, acrylic acid, maleic acid, and fumaric acid, and may include all the structures. More preferred. This is because there are two types of viruses with and without envelope, and it is considered that the structures of antibacterial agents and antiviral agents that can effectively inhibit the activity of each type are different.
Therefore, for example, if the effect of only influenza virus, which is a non-enveloped virus, is expected, only the styrene polymer derivative compound may be contained, and among them, the effect may be sufficiently obtained if only the styrene resin alone is contained.

As the inorganic antibacterial agent and antiviral agent, silver antibacterial agents and antiviral agents are preferable from the viewpoint of non-biotoxicity and excellent safety, among which phosphate-based glass-silver-supporting compounds, silver zeolite compounds, and silver zeolite compounds, and The molybdenum oxide silver double salt compound is more preferable because it exhibits antibacterial and antiviral properties even in a small amount and can suppress the addition amount.
The average particle size of the inorganic antibacterial agent or antiviral agent is preferably 0.1 to 10 μm, for example.
With the average particle size, the antibacterial agent and the antiviral agent can be preferably dispersed, and the antibacterial and antiviral properties can be suitably imparted without causing unevenness.

When the silver-based antibacterial agent or antiviral agent is added to the surface protective layer, the color changes depending on the surface protective layer (when the color is changed by heat or light in the state of the added paint, or after the surface protective layer is formed. The color may change due to heat or light), but in this case, it can be improved by adding an ultraviolet inhibitor, a light stabilizer, or the like in a timely manner.
For example, when a benzotriazole compound is used for the molybdenum oxide silver double salt compound, a discoloration improving effect can be expected.

The content of the antibacterial agent and the antiviral agent is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

The 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.
The antiallergen agent may be an antibacterial agent or an antiviral agent.

The inorganic compound is preferably a material that supports a metal.
As the material supporting the metal, for example, 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 is preferable, and among them, oxidation Titanium, zirconium phosphate and the like are preferable.
As the metal supported on the material supporting the metal, for example, at least one selected from the group consisting of gold, silver, platinum, zinc and copper is preferable, and among these, silver, zinc and the like are preferable.
As commercially available products, for example, "Parafine ANV-100: silver-supported inorganic compound" manufactured by Ohara Palladium Co., Ltd., "Atomy Ball TZ-R: zinc-supported on titanium oxide" manufactured by JGC Catalysts and Chemicals, etc. can be preferably used. , This anti-allergen agent acts effectively against various allergens such as mites and pollen.

The organic compound is at least one monomer selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, styrene sulfonic acid and a salt thereof. It is preferably a polymer containing components.

Examples of the water-insoluble polymer containing a phenolic hydroxyl group include "Allerbuster (trade name)" manufactured by Sekisui Chemical Co., Ltd. and "Marcalinker M (trade name)" manufactured by Maruzen Petroleum Co., Ltd. as commercial products. Can be used.

Examples of the polyphenol compound supported on the inorganic solid acid include a combination of a polyphenol compound and a zirconium compound, and a commercially available product thereof is "Allelimve (trade name)" manufactured by Toa Synthetic Co., Ltd. And so on. These anti-allergen agents act effectively against various allergens such as mites and pollen.

As the styrene sulfonic acid and a salt thereof, a material as shown in Patent No. 6136433 can be used, and preferred examples thereof include a homopolymer of styrene sulfonate and a styrene sulfonate-styrene sulfonic acid co-weight. Examples thereof include coalescence, styrene sulfonate-styrene copolymer, styrene sulfonic acid-styrene copolymer and styrene sulfonate-styrene sulfonic acid-styrene ternary copolymer.

The anti-allergen agent may be a mixture of an organic compound and an inorganic compound, and examples thereof include a mixture of an anionic phenol-based material and a zinc-based material having anti-allergen properties.

Examples of the anionic phenolic material include tannin, tannic acid / sulphate, phenylsulfonic acid formaldehyde resin, noboratsk type resin sulfone compound, noboratsk type resin methanesulfonic acid, resol type resin methanesulfonic acid, and benzylated phenol. Examples thereof include sulfonic acids, thiophenol-based compounds, dihydrooxy, di-phenylsulfone-based compounds, ligant compounds, and metal chelate compounds thereof.

The zinc-based material is appropriately selected from a water-soluble zinc compound, a water-insoluble zinc compound, a zinc / metal oxide composite material, and the like, and is a composite particle of the water-insoluble zinc compound and / or the water-insoluble zinc / metal oxide. Is water-dispersed, the average particle size is 50 μm or less, and the metal oxide preferably contains at least one of titania, silica, and alumina.

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

As the electron beam source of ionizing radiation, for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamistron type, and high frequency type are used. It can be used to irradiate electrons with an energy of 70 to 1000 keV. The irradiation dose of the electron beam is preferably, for example, about 1 to 10 mad.
As the ultraviolet source of the ionized radiation, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, or a metal halide lamp can be used, and the wavelength of the ultraviolet rays is usually 190 to 380 nm. The wavelength range is mainly used.

The thickness of the surface protective layer is not particularly limited, but the preferable lower limit is 0.1 μm, the preferred 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 surface protective layer is less than 0.1 μm, sufficient durability (scratch resistance, stain resistance, weather resistance, etc.) may not be imparted, and if it exceeds 50 μm, the transparency of the present invention is obtained. The transmittance of the sex resin film may decrease, and the visibility of the pattern in the pattern layer may decrease.

The surface protective layer is a layer having a side surface opposite to the side surface to be laminated on the pattern layer described later, and is preferably adhered to the transparent resin layer via a primer. By using the primer, the adhesiveness between the surface protective layer and the transparent resin layer can be further strengthened.
As the primer, the same primer as the adhesive primer layer described later can be preferably used.

(Concave and convex shape)
The transparent resin film of the present invention has an uneven shape on the surface protective layer side.
The method for forming the uneven shape is not particularly limited, and examples thereof include a method of embossing with heat and a method of transferring the uneven shape by a shaping sheet.
Examples of the heat embossing include a method of embossing with a well-known single-wafer or rotary embossing machine.
Examples of the embossed pattern include sand grain, hairline, satin finish, wood grain conduit groove, stone plate surface unevenness, cloth surface texture, and perennial groove.
Also. The temperature at the time of embossing is not particularly limited, but a temperature at which the so-called embossing return, in which the uneven pattern disappears during heat pressure bonding, is preferable.
The depth of the uneven shape to be formed is not particularly limited, but for example, the center line average roughness Ra defined in JIS B 0601 (1982) may be appropriately adjusted to be within the range of 1 to 30 μm. preferable.

The thickness of the transparent resin film of the present invention is not particularly limited, but the thickness of the concave-convex concave portion is 100 μm or more. If the thickness of the concave-convex concave portion of the transparent resin film is less than 100 μm, sufficient durability (wear resistance, scratch resistance) cannot be imparted to the transparent resin film of the present invention, and the concave-convex shape of the transparent resin film The amount of the ultraviolet absorber contained in the recess becomes insufficient, and sufficient weather resistance cannot be obtained. The thickness of the concave-convex concave portion 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 and convex concave portions.
Here, the above-mentioned "concave-convex-shaped recess" refers to the thinnest portion of the thickness of the transparent resin film of the present invention, and as shown in FIG. 1, the most concavo-convex shape of the surface protective layer 11. It is a portion including a deep recess, and can be confirmed by observing the cross section of the transparent resin film of the present invention under a microscope. The length from the bottom of the deepest recess to the side surface of the transparent resin layer 12 opposite to the surface protection layer 11 side is the "thickness of the concave recess".
The upper limit of the thickness of the concave-convex concave portion of the transparent resin film is not particularly limited, but is preferably less than 500 μm, for example.
Further, as shown in FIG. 1, the length from the surface of the surface protective layer 11 to the side surface of the transparent resin layer 12 opposite to the surface protective layer 11 side is the total thickness of the transparent resin film 10 of the present invention. The preferred lower limit of the total thickness is 100 μm, the preferred upper limit is 500 μm, the more preferred lower limit is 140 μm, and the more preferred upper limit is 460 μm.

(UV 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. Of these, an organic ultraviolet absorber having excellent transparency is preferably used.
Examples of the organic ultraviolet absorber include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3'. -Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2) 2 such as'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, etc. '-Hydroxyphenyl-5-chlorobenzotriazole UV absorbers, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5' -Methylphenyl) Benzotriazole-based UV absorbers such as 2'-hydroxyphenylbenzotriazole-based UV absorbers such as benzotriazole, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4, 2,2'-Dihydroxybenzophenone-based UV absorbers such as 4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxy Examples thereof include benzophenone-based ultraviolet absorbers such as 2-hydroxybenzophenone-based ultraviolet absorbers such as benzophenone, and salicylic acid ester-based ultraviolet absorbers such as phenyl sulcylate and 4-t-butyl-phenyl-salicylate.
Of these, a triazine-based ultraviolet absorber is preferable from the viewpoint of preferably imparting weather resistance, design, bleeding suppression, and the like.

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, 4,4', 4''-(1,3,5-Triazine-2,4,6-triyltriimino) Tris benzoate Tris (2-ethylhexyl), 2- (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-triazine-2-yl) ) -5- [2- (2-Ethylhexanoyloxy) ethoxy] phenol and the like.
In addition, a reactive ultraviolet absorber or the like in which an acryloyl group or a methacryloyl group is introduced into the benzotriazole skeleton can also be used. Alternatively, if high transparency is not required, an inorganic ultraviolet absorber can be added. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, iron oxide, zinc oxide or the like having a particle size of 0.2 μm or less can also be used.

The content of the ultraviolet absorber is appropriately determined by the ultraviolet absorbing ability of the ultraviolet absorber used.
For example, when a triazine-based ultraviolet absorber is contained in the transparent resin layer as the 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, weather resistance may not be sufficiently imparted, and if the content in the transparent resin layer exceeds 10% by mass, the transparency of the film may not be sufficiently imparted. The designability of the transparent resin film of the present invention is deteriorated when the film is used as a decorative board, and the adhesiveness between the transparent resin film of the present invention and the pattern layer described later is not sufficiently obtained. It may decrease.
The more preferable lower limit of the content of the ultraviolet absorber is 2% by mass, and the more preferable upper limit is 7% by mass.

Since the transparent resin film of the present invention can have extremely excellent weather resistance, it is preferable that the ultraviolet absorber is contained in the surface protective layer and / or the transparent resin layer.
In the conventional transparent resin film, if the layer having the uneven shape contains the ultraviolet absorber, the amount of the ultraviolet absorber may be small due to the difference in thickness, so that sufficient weather resistance cannot be obtained. Although it has existed, the transparent resin film of the present invention is expensive because the concave-convex-shaped recesses have a predetermined thickness as described above and the concave-convex-shaped recesses also sufficiently contain an ultraviolet absorber. Weather resistance can be obtained.
Further, when the above-mentioned primer layer is provided between the transparent resin layer and the surface protective layer, the primer layer may contain an ultraviolet absorber.

(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 surface of the transparent resin layer 12 opposite to the surface protective layer 11 side.
The adhesive primer layer is a layer provided to further strengthen the adhesiveness between the base material having the pattern layer described later and the transparent resin film of the present invention laminated via the adhesive layer.

The adhesive primer layer preferably contains a binder resin.
Examples of the binder resin include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose-based resin, polyester resin, vinyl chloride-vinyl acetate copolymer and the like. Urethane resin is preferable because of its adhesiveness to the adhesive layer described later and efficiency during production.

The thickness of the adhesive primer layer is preferably 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 on which the pattern layer described later is laminated can be suitably secured, and if it is 10 μm or less, the transparent resin film of the present invention is thick. Sufficient transparency can be obtained without becoming too much, and the design of the decorative board can be preferably ensured.
The thickness of the adhesive primer layer is more preferably 0.8 μm or more and 6 μm or less.
The adhesive primer layer may contain inorganic fine particles such as silica.

In the present invention, the transparent resin layer is subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma treatment, ultraviolet (UV) treatment, and flame treatment within a range not deviating from the gist of the present invention. You may.

As for the various additives added to each layer of the transparent resin film (inorganic filler added to the primer layer and the surface protection layer, etc.), it is preferable that the various additives are vesicled. The method for vesicle-forming various additives is not particularly limited, and vesicles can be formed by a known method, and the supercritical reverse-phase evaporation method is particularly preferable.

Other examples of the vesicle treatment method include a Bangham method, an extrusion method, a hydration method, a reverse phase evaporation method, and a freeze-thaw method.
Briefly explaining such a vesicle treatment method, in the above Bangham method, chloroform or chloroform / methanol mixed solvent is put in a container such as a flask, and phospholipid is further put in and dissolved. Then, the solvent is removed using an evaporator to form a thin film composed of lipids, a dispersion liquid of additives is added, and then hydrated and dispersed with a vortex mixer to obtain vesicles.
The extrusion method is a method in which a thin-film phospholipid solution is prepared and passed through a filter instead of the mixer used as an external perturbation in the Bangham method to obtain a vesicle.
The hydration method is almost the same preparation method as the Bangham method, but is a method of obtaining a vesicle by gently stirring and dispersing without using a mixer.
In the reverse phase evaporation method, phospholipids are dissolved in diethyl ether or chloroform, a solution containing additives is added to form a W / O emulsion, the organic solvent is removed from the emulsion under reduced pressure, and then water is added. It is a method of obtaining vesicles by doing so.
The freeze-thaw method is a method of using cooling / heating as an external perturbation, and is a method of obtaining a vesicle by repeating this cooling / heating.

Hereinafter, the supercritical reverse phase evaporation method will be described in detail.
The supercritical reverse phase evaporation method is water-soluble or hydrophilic in a mixture in which a substance forming an outer film of a vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure condition above the supercritical point. This is a method in which an aqueous phase containing various additives as a sex encapsulant is added to form a capsule-shaped vesicle containing various additives as an encapsulant in a single layer film.
The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and is a temperature above the critical point or higher. Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained.
In general, vesicles are a general term for vesicles having a spherical shell-like closed membrane structure containing a liquid phase, and in particular, liposomes whose outer membrane is composed of biolipids such as phospholipids. ..

Examples of the phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin and other glycerophospholipids, and sphingomyelin. , Ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

As the substance constituting the outer membrane, a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.

Examples of the nonionic surfactant include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene-. One or two types such as polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The above can be used.

Examples of the cholesterol include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like. Can be used.

The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present invention, by forming the outer membrane into liposomes formed from phospholipids, the compatibility between the resin composition which is the main component of each layer and various additives can be improved.

<Veneer>
Since 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, it imparts excellent designability to the decorative board on which the transparent resin film of the present invention is laminated. You can also do it.
Such a decorative board including the base material, the pattern layer, and the transparent resin film of the present invention in order in the thickness direction is also one aspect of the present invention.

Next, a preferable example of the decorative board of the present invention will be described with reference to FIG.
In the decorative board 20 of the present invention, the pattern layer 24 is laminated on one surface of the base material 25, and the transparent resin film 10 of the present invention is laminated on the side of the pattern layer 24 opposite to the side having the base material 25. There is.
Further, it is preferable to have the adhesive layer 23 from the viewpoint of further strengthening the adhesiveness between the pattern layer 24 and the transparent resin film 10 of the present invention.
Hereinafter, each configuration of the decorative board of the present invention will be described.

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

The material constituting the 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 base material, a resin material or a wood-based material having rigidity and lightness is preferable. Further, these composite materials may be used.
As the resin material, for example, it is preferable to contain a thermoplastic resin.
Examples of the thermoplastic resin include polyvinyl chloride resins such as polyvinyl chloride resin, polyvinyl acetate resin and polyvinyl alcohol resin, polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene- (meth) acrylic acid. Polyethylene resin such as based resin, polyester resin such as polyethylene terephthalate resin (PET resin), acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, polychloride Single or copolymer of thermoplastic resin such as vinyl resin plate, diene rubber such as styrene butadiene rubber, isoprene rubber, chloroprene rubber, non-diene rubber such as butyl rubber and ethylene propylene rubber, natural rubber, thermoplastic elastomer or These mixed resins are preferably mentioned. Of these, polyolefin resins, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, ionomers and the like are preferable. Further, the resin material may be foamed.

Thermoplastic resin plates and thermosetting resin plates can be used as necessary, such as colorants (pigments or dyes), fillers such as wood powder and calcium carbonate, matting agents such as silica, foaming agents, flame retardants, and talc. Various additives such as lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be contained.

Examples of the wood-based material include various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melamy, and the core material includes veneer and wood single made from these materials. Any of board, wood plywood (including LVL), particle board, medium density fiberboard (MDF), high density fiberboard (HDF), veneer, etc., or a laminated material in which these are appropriately laminated may be used. ..
Examples of the metal material include iron, aluminum and the like.
Moreover, the said base material may contain an inorganic compound.

Further, the base material may contain the above-mentioned flame retardant. By containing a flame retardant, the flame retardancy of the base material is further improved.

When the base material has a base material made of a plurality of resins, the types of resins forming the base material made of the plurality of resins may be the same or different, and a group made of a plurality of resins. The thickness of the materials may be the same or different.

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.

The thickness of the base material is not particularly limited, and is preferably 0.01 mm or more, more preferably 0.1 mm or more and 50 mm or less, for example.
It should be noted that the base material includes a substantially plate-like material other than a planographic plate, and also includes a material having irregularities and curved surfaces.

(Pattern layer)
The base material has a pattern layer laminated on one side.
The pattern layer is a layer that imparts decorativeness to the decorative board of the present invention made of the transparent resin film of the present invention, and may be, for example, a uniformly colored concealing layer (solid printing layer). , It may be a pattern layer formed by printing various patterns using ink and a printing machine, or it may be a layer in which a concealing layer and a pattern layer are combined (hereinafter, a pattern layer). ..

By providing the concealing layer, when the above-mentioned base material is colored or has uneven color, it is possible to give an intended color and adjust the surface color.
In addition, by providing the above pattern layer, stone patterns that imitate the surface of rocks such as wood grain patterns and marble patterns (for example, Travertin marble patterns), fabric patterns that imitate textures and cloth-like patterns, tiled patterns, and bricks It is possible to add a pattern such as a stack pattern or a combination of these to a decorative sheet such as parquet, patchwork, characters, symbols, abstract patterns, flower patterns, landscapes, and characters. These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing plates of the individual colors that make up the pattern. Will be done.

As the ink composition used for the pattern layer, a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is used. The binder resin is not particularly limited, and for example, urethane resin, acrylic resin, urethane-acrylic resin, urethane-acrylic copolymer resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic common weight. Combined resin, acrylic resin, polyester resin, nitrocellulose resin and the like are preferably mentioned. As the binder resin, any one of these can be used alone or in combination of two or more.
The colorants include carbon black (black), iron black, titanium white, antimony white, chrome yellow, titanium yellow, petals, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, and isoindolinone. Organic pigments such as yellow and phthalocyanine blue, metal pigments made of scaly foil pieces such as dyes, aluminum and brass, titanium dioxide-coated mica, pearl gloss pigments made of scaly foil pieces such as basic lead carbonate, etc. Is preferably mentioned.

The thickness of the pattern layer is not particularly limited, and is preferably 0.1 μm or more, more preferably 0.5 μm or more and 600 μm or less, for example. When the thickness of the pattern layer is within the above range, an excellent design can be imparted to the decorative board of the present invention, and concealment can be imparted.
If the base material itself has a design property such as a veneer, the pattern layer may not be provided.

The thickness of the decorative board of the present invention is not particularly limited, and is preferably 0.05 mm or more, more preferably 1 mm or more and 50 mm or less, for example.

(Adhesive layer)
The decorative board of the present invention preferably has an adhesive layer between the pattern layer and the transparent resin film of the present invention.
The adhesive layer is a layer provided between the pattern layer and the base sheet of the transparent resin film of the present invention. By having the adhesive layer, the pattern layer and the transparency of the present invention are transparent. The adhesiveness with the sex resin film can be further strengthened.

The adhesive layer preferably contains a binder resin.
As the binder resin contained in the adhesive layer, the binder resin used in the adhesive primer layer described above can be preferably used.
The method of attaching the adhesive layer is not particularly limited, and for example, a heat melting method, a heat laminating method, a water-based adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot melt adhesive, or the like is used. It can be obtained by laminating.

(Manufacturing method of decorative board)
Examples of the method for producing a decorative board of the present invention include a method of laminating the base material, the pattern layer, and the transparent resin film by using the adhesive or the like for forming the adhesive layer described above.
Among them, in the method for manufacturing the decorative board, the 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 the transparent via the adhesive layer. It is preferable to have a step of adhering the sex resin film and the pattern layer.
Such a method for producing a decorative board of the present invention is also an aspect of the present invention.
In the transparent resin film, when the uneven shape is formed on the surface protective layer side, the uneven shape is formed by embossing or the like, but the uneven shape on the embossed surface side is followed. Some uneven shape is also formed on the surface opposite to the embossed surface (the side laminated on the pattern layer). In such a case, so-called air shavings, in which air enters the uneven shape on the side to be laminated on the pattern layer formed on the transparent resin film, may occur, and the design may be deteriorated.
Since the method for producing a decorative board of the present invention includes 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, the concave-convex shape on the side to be laminated on the pattern layer is formed. The adhesive layer can also enter the recesses, preventing the above-mentioned occurrence of air shavings and suppressing deterioration of the design.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Example 1)
A transparent polypropylene film (thickness 60 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name: Adecaster LA-46, manufactured by ADEKA) is prepared, and isocyanate is used as a curing agent on one surface of the transparent polypropylene film. An adhesive primer, which is a two-component effect type urethane resin, was applied to provide an adhesive primer layer having a thickness of 2 μm.
Next, a flame retardant (metal phosphinate) containing 5% by mass of a triazine-based ultraviolet absorber (product name: ADEKA STAB LA-46, manufactured by ADEKA) on the other surface of the transparent polypropylene film (opposite surface of the primer layer for adhesion). A transparent polypropylene resin (thickness 80 μm) containing a salt-based flame retardant, product name Pekoflam STC, manufactured by Arkroma Co., Ltd. was melt-extruded and laminated by a thermal laminating method to obtain a transparent resin layer having a two-layer structure.
The content of the flame retardant was 100 parts by mass for the flame retardant-containing transparent polypropylene resin and 6 parts by mass for the metal phosphinic acid salt flame retardant.
The thickness of the two-layer transparent resin layer is 140 μm, and the content of the phosphinic acid metal salt-based flame retardant is 3.3, assuming that the total mass of the two-layer transparent resin layer is 100% by mass. It was% by mass.
After corona treatment was applied to the surface of the flame retardant-containing transparent polypropylene resin, a primer layer, which is a two-component effect urethane resin using isocyanate as a curing agent, was applied so as to have a thickness of 2 μm.
On the surface of the primer layer, urethane (meth) acrylate, which is an ionizing radiation curable resin containing 5% by mass of a triazine-based ultraviolet absorber (product name: ADEKA STAB LA-46, manufactured by ADEKA), has a thickness of 15 μm. After coating by the gravure coating method, an electron beam was irradiated under the condition of an acceleration voltage of 165 keV and 5 mad to form a surface protective layer.
Immediately after heating the surface protective layer side with an infrared non-contact type heater, embossing by heat pressure was performed to shape the uneven shape, and a transparent resin film was prepared. The obtained transparent resin film had a total thickness of 159 μm and a concave-convex concave portion having a thickness of 105 μm.
On the other hand, an HDF (high density fiberboard) (thickness 3 mm) was prepared, and a picture layer was provided on one surface of the HDF with an inkjet printer so as to have a thickness of 2 μm to prepare a base material.
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 adhesive primer layer side of the obtained transparent resin film and the adhesive primer layer side. A decorative board was produced by laminating so that the pattern layer side of the base material and the provided surface were in contact with each other. Then, a pressure of 10 kg / m ² was applied and the mixture was cured in a normal temperature environment for 3 days.

(Example 2)
A transparent resin film similar to 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, Ravitor FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.). And a veneer was made.
The content of the phosphazene-based flame retardant was 3.1% by mass, where the total mass of the two-layer transparent resin layer was 100% by mass.

(Example 3)
A transparent polypropylene resin containing a flame retardant (phosphazene flame retardant, Ravitor FP-10, manufactured by Fushimi Pharmaceutical Co., Ltd.) and hydrophilic fumed silica (AEROSIL 50 manufactured by Nippon Aerosil Co., Ltd.) as a transparent polypropylene resin to be melt-extruded. A transparent resin film was prepared in the same manner as in Example 2 except that a resin (thickness: 30 μm, transparent resin layer) was used, and a decorative material was prepared in the same manner as in Example 1.
The contents of the flame retardant and the hydrophilic fumed silica were set to 6 parts by mass, respectively, with the mass of the flame retardant-containing transparent polypropylene resin being 100 parts by mass.
The thickness of the two-layer transparent resin layer is 140 μm, and the contents of the flame retardant and the hydrophilic fumed silica are 3 respectively, assuming that the total mass of the two-layer transparent resin layer is 100% by mass. It was 1% by mass.

(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 to be melt-extruded did not contain a flame retardant.

(Comparative Example 2)
A transparent polypropylene film (thickness 60 μm) containing 5% by mass of a triazine-based ultraviolet absorber (product name Adecastab LA-46, manufactured by ADEKA) and a triazine-based ultraviolet absorber (product name Adecastab LA-46, manufactured by ADEKA). The same as in Example 1 except that a flame-retardant-containing transparent polypropylene resin (thickness 60 μm) containing 5% by mass of the transparent resin film was used and the concave-convex shape of the transparent resin film was 90 μm depending on the uneven shape. To prepare a transparent resin film and a decorative board.

(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 adhesive primer was 13 μm.

(Example 5)
Transparency as in Example 1 except that 3 parts by mass of a phosphoric acid-based glass silver-supporting compound (manufactured by Koa Glass / PG-711) was added to 100 parts by weight of the ionizing radiation curable resin as an antiviral agent. A resin film and a decorative board were produced.

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

(Evaluation method)
<Design>
The printed patterns of the decorative boards obtained in Examples and Comparative Examples 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 looks slightly cloudy-: The printed pattern is not clearly visible

<Color difference after weathering test>
The decorative boards obtained in Examples and Comparative Examples were put into a super-accelerated weather resistance tester (Iwasaki Electric Co., Ltd. Eye Super UV Tester) set under the following conditions, and 20-hour irradiation and 4-hour dew condensation were set as one cycle. After 17 cycles of operation, it was taken out.
(Promotion test conditions)
・ Black panel temperature: 63 ℃
・ Humidity: 50% RH
-Irradiant intensity: 60 W / m ² (365 nm)
Then, the change in color difference of the decorative sheet before and after the above acceleration 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 acceleration test were measured, 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 equation 1
++: ΔE <1.0
+: 1.0 ≤ ΔE <1.5
-: ΔE ≧ 1.5
ΔL = | L value (after weather resistance test) -L value (before weather resistance test) |
Δa = | a value (after weather resistance test) -a value (before weather resistance test) |
Δb = | a value (after weather resistance test) -a value (before weather resistance test) |

<Abrasion resistance (Taber wear test)>
The decorative boards obtained in Examples and Comparative Examples were subjected to the Japanese Agricultural Standards for Flooring; Wear A Test, and were loaded with 1 kg using a Taber type wear tester (manufactured by Rigaku Kogyo Co., Ltd.) wear paper (S-42). A test was carried out, and the pattern residue of the pattern pattern layer when rotated 1500 times 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

<Flame retardancy evaluation>
[Horizontal flammability (flame retardancy: difficulty of spreading fire)]
The decorative board was cut into a size of 9 cm × 30 cm and used as a test piece. As shown in FIGS. 4A and 4B, a metal rectangular base 103 is placed on a base 102 of a commercially available household heater 101 (voltage AC100V, power consumption 1200W), and the metal is installed on the base. A test piece 105 was placed in a frame 104 made of metal, the heater angle was adjusted to 45 °, and the heater output was adjusted to 4/5 output to test the difficulty of spreading the fire. Specifically, the test piece was preheated for 2 minutes using the above household heater. Next, as shown in FIG. 4A, the end 106 on the heater side in the longitudinal direction of the test piece is heated with a lighter 107 for 1 minute to ignite, and then, as shown in FIG. 4B, the longitudinal direction of the test piece 105 is ignited. The fire spread to. Next, the fire spread state was visually observed, and the combustion distance (L1) was evaluated as follows. The results are shown in Table 1.
[Combustion distance (L1)]
The fire spread distance from the initial ignition, excluding the lighter's fire after igniting the test piece, was measured and used as the fire spread distance (L1), which was evaluated 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

<Antiviral>
The transparent resin films prepared in Examples 1 and 5 were subjected to an antiviral performance test by a method based on 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 2.0 or more-: Antiviral activity value less than 2.0

<Anti-allergenicity>
The transparent resin films prepared in Examples 1 and 6 were finely cut and the amount of allergen after being immersed in an aqueous mite allergen solution for 1 day was visually confirmed by a horizontal development chromatography method (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 could not be confirmed.

It was confirmed that the decorative board according to the example had excellent design properties, and was also excellent in weather resistance and flame retardancy. Further, from Example 3, the design property is improved by containing the flame retardant and the filler in the thermoplastic resin layer, and from Example 1, the design property is improved by having the adhesive primer layer having a predetermined thickness. Was confirmed to improve.
On the other hand, in Comparative Example 1 using a transparent resin film containing no flame retardant, the flame retardancy was inferior, and in Comparative Example 2 in which the thickness of the concave-convex concave portion was less than 100 μm, weather resistance and abrasion resistance Was inferior in.
From Table 4, it was confirmed that the transparent resin film produced in Example 5 had antiviral properties.
From Table 5, it was confirmed that the transparent resin film produced in Example 6 had anti-allergenic properties.

According to the present invention, it is possible to provide a transparent resin film which can impart excellent designability to a decorative board and also has excellent weather resistance and flame retardancy. Since the decorative board of the present invention has excellent design and weather resistance, it can be used for interior building materials such as doors such as fittings and sliding doors, flooring agents, walls, ceilings, and various decorative molded bodies. It is preferably used.

10 Transparent resin film 11 Surface protective 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 Household heater stand 103 Rectangular stand 104 Metal Frame 105 Test piece 106 End 107 Lighter

Claims (13)

A transparent resin film for protecting the pattern layer laminated on one of the base materials.
The transparent resin film has at least a surface protective layer and a transparent resin layer laminated on each other.
It has an uneven shape on the surface protection layer side.
The thickness of the concave-convex concave portion of the transparent resin film is 100 μm or more.
The transparent resin film is a transparent resin film containing an ultraviolet absorber and a flame retardant. The transparent resin film according to claim 1, wherein the ultraviolet absorber is contained in the surface protective layer and / or the transparent resin layer. The transparent resin film according to claim 1 or 2, which has an adhesive primer layer on the side opposite to the surface protective layer side of the transparent resin layer. 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. The transparent resin film according to claim 1, 2, 3, or 4, wherein the ultraviolet absorber is a triazine-based ultraviolet absorber. The transparent resin film according to any one of claims 1 to 5, wherein the transparent resin layer contains a flame retardant. The transparent resin film according to any one of claims 1 to 6, wherein the surface protective layer contains a flame retardant. The transparent resin film according to any one of claims 1 to 7, wherein the surface protective layer contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent. The transparent resin film according to claim 6 or 7, wherein the flame retardant is at least one selected from the group consisting of a phosphinic acid metal salt-based flame retardant, a phosphazene-based flame retardant, and a NOR-type hindered amine-based flame retardant. The transparent resin film according to any one of claims 1 to 9, wherein the transparent resin layer contains a filler. A decorative board comprising, in order in the thickness direction, a base material, a pattern layer, and the transparent resin film according to any one of claims 1 to 10. The decorative board according to claim 11, which has an adhesive layer between the pattern layer laminated on one of the base materials and the transparent resin film. The method for manufacturing a decorative board according to claim 11 or 12.
The process of forming an adhesive layer on the surface to be laminated on the pattern layer of the transparent resin film, and
A method for producing a decorative board, which comprises a step of adhering the transparent resin film and the pattern layer via the adhesive layer.

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