WO2021205842A1 - 透明性樹脂フィルム、透明性樹脂フィルムの製造方法、化粧板、及び、化粧板の製造方法 - Google Patents
透明性樹脂フィルム、透明性樹脂フィルムの製造方法、化粧板、及び、化粧板の製造方法 Download PDFInfo
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- WO2021205842A1 WO2021205842A1 PCT/JP2021/011213 JP2021011213W WO2021205842A1 WO 2021205842 A1 WO2021205842 A1 WO 2021205842A1 JP 2021011213 W JP2021011213 W JP 2021011213W WO 2021205842 A1 WO2021205842 A1 WO 2021205842A1
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- Prior art keywords
- transparent resin
- layer
- resin film
- transparent
- flame retardant
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- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0875—Treatment by energy or chemical effects by wave energy or particle radiation using particle radiation
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
Definitions
- the present invention relates to a transparent resin film, a method for producing a transparent resin film, a decorative board, and a method for producing a decorative board.
- a transparent resin film is laminated to impart surface performance.
- a weather resistant agent may be added to the layer constituting the transparent resin film.
- Patent Document 1 an overlaminate formed by laminating a protective layer on one surface and an adhesive layer on the other surface of a transparent polypropylene resin film having a thickness of 40 to 100 ⁇ m and containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer. The film for use is disclosed. Further, Patent Document 1 discloses that an ionizing radiation curable resin is used as the protective layer.
- Patent Document 1 discloses that the printed surface is protected from light to prevent fading, it is not considered to form an uneven shape on the surface of the overlaminate film, and it has been required in recent years. It did not have a design.
- the transparent resin film has a layer to which a weathering agent is added
- the layer containing the weathering agent turns yellow depending on the type of the weathering agent, and the design There was also a problem that the sex was reduced.
- the present invention solves the above-mentioned problems, has excellent designability by having an uneven shape, and even if it is irradiated with an electron beam during production while imparting weather resistance.
- An object of the present invention is to provide a transparent resin film capable of suppressing yellowing and preventing deterioration of design.
- the present inventors have diligently studied to solve the above-mentioned problems, and in a transparent resin film for protecting the pattern layer laminated on one of the base materials, on the side opposite to the side laminated on the pattern layer. It has an uneven shape, and at least a transparent resin layer and a transparent surface protective layer made of an ionizing radiation curable resin are laminated in this order, and the transparent resin layer and / or the transparent surface protective layer
- a triazine-based ultraviolet absorber it has excellent designability, and while imparting weather resistance, it suppresses yellowing due to electron beams when curing an ionizing radiation curable resin. , It has been found that the deterioration of the design can be prevented, and the present invention has been completed.
- the transparent resin film of the present invention is a transparent resin film for protecting the pattern layer laminated on one of the base materials, and has an uneven shape on the side opposite to the side laminated on the pattern layer. At least the transparent resin layer and the transparent surface protective layer are laminated in this order, and the transparent surface protective layer is made of an ionizing radiation curable resin, and the transparent resin layer and / or the above.
- the transparent surface protective layer is characterized by containing a triazine-based ultraviolet absorber.
- the thickness of the concave-convex concave portion is preferably 80 ⁇ m or more.
- the transparent resin film of the present invention has a concavo-convex shape on the side where the pattern layers are laminated, and Rzmax defined by JIS B 0601 (2001) having a concavo-convex shape on the side where the pattern layers are laminated. , 80 ⁇ m or less is preferable.
- the transparent resin layer is preferably made of a thermoplastic resin.
- the transparent resin layer preferably has at least two layers.
- the transparent resin layer preferably contains a flame retardant.
- the transparent surface protective layer preferably contains a flame retardant.
- the layer containing the flame retardant preferably contains a filler.
- the flame retardant is preferably at least one selected from the group consisting of a metal salt-based phosphinic acid flame retardant, a phosphazene-based flame retardant and a NOR-type hindered amine-based flame retardant.
- the transparent surface protective layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent.
- the decorative board is provided with the transparent resin film and the base material provided with the pattern layer.
- the method for producing a transparent resin film of the present invention is a preparatory step of preparing a transparent resin layer containing a triazine-based ultraviolet absorber, and a coating in which an ionizing radiation curable resin is applied to one surface of the transparent resin layer. It is characterized by having a step and an irradiation step of irradiating the ionizing radiation curable resin with an electron beam.
- the preparatory step is preferably a step of preparing a thermoplastic resin and laminating a thermoplastic resin containing a triazine-based ultraviolet absorber on one of the thermoplastic resins to obtain a transparent resin layer.
- the ionizing radiation curable resin preferably contains a triazine-based ultraviolet absorber.
- the method for producing a decorative board of the present invention is a method for manufacturing a decorative board including a base material on which a pattern layer is laminated and the transparent resin film of the present invention in this order, wherein the pattern layer of the transparent resin film is It is characterized by having a step of forming an adhesive layer on the surface on the side to be laminated and a step of adhering the transparent resin film and the pattern layer via the adhesive layer.
- Having an uneven shape has excellent designability, and while imparting weather resistance, it suppresses yellowing even when irradiated with an electron beam during manufacturing, and prevents deterioration of designability. It is possible to provide a transparent resin film capable of providing a transparent resin film.
- FIG. 1 is a cross-sectional view schematically showing an example of the transparent resin film of the present invention.
- FIG. 2 is a cross-sectional view schematically showing a preferable example of the transparent resin film of the present invention.
- FIG. 3 is a schematic view illustrating the thickness of the concave-convex concave portion of the transparent resin film.
- FIG. 4 is a schematic view illustrating the thickness of the concave-convex concave portion of the transparent resin film.
- FIG. 5 is a cross-sectional view schematically showing an example of a decorative board.
- 6 (a) and 6 (b) are schematic views for explaining a method for evaluating flame retardancy.
- the transparent resin film of the present invention is a transparent resin film for protecting the pattern layer laminated on one of the base materials, and has an uneven shape on the side opposite to the side laminated on the pattern layer. At least the transparent resin layer and the transparent surface protective layer are laminated in this order, and the transparent surface protective layer is made of an ionizing radiation curable resin, and the transparent resin layer and / or the transparent surface.
- the surface protective layer is characterized by containing a triazine-based ultraviolet absorber.
- FIG. 1 is a cross-sectional view schematically showing an example of the transparent resin film of the present invention.
- the transparent resin film 10 of the present invention at least the transparent resin layer 1 and the transparent surface protective layer 2 are laminated in this order, and the transparent surface protective layer 2 is made of an ionizing radiation curable resin and is transparent.
- the sex resin layer 1 and / or the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber.
- FIG. 2 is a cross-sectional view schematically showing a preferable example of the transparent resin film of the present invention.
- the transparent resin layer 1 preferably has a two-layer structure having a transparent resin layer 1a and a transparent resin layer 1b. Further, it is preferable to have the adhesive primer layer 3 on the side opposite to the transparent surface protective layer 2 side of the transparent resin layer 1.
- each configuration will be described.
- the transparent resin film 10 of the present invention has a transparent resin layer 1.
- the transparent resin layer 1 is not particularly limited as long as the pattern layer provided on the base material can be seen, and includes any of colorless transparent, colored transparent, translucent, etc., and the material is not limited, but contains a thermoplastic resin. Is preferable.
- thermoplastic resin examples include low-density polyethylene (including linear low-density polyethylene), medium-density polyethylene, high-density polyethylene, ethylene- ⁇ -olefin copolymer, homopolypropylene, polymethylpentene, polybutene, and ethylene-propylene co-weight.
- Olefin-based thermoplastic resins such as coalescence, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, or a mixture thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate.
- thermoplastic ester-based resins such as polycarbonate and polyarylate, acrylic thermoplastics such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, butyl polyacrylate and the like.
- acrylic thermoplastics such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, butyl polyacrylate and the like.
- resins polyamide-based thermoplastic resins such as nylon-6 and nylon-66, polyimides, polyurethanes, polystyrenes, acrylonitrile-butadiene-styrene resins, ionomers, and polyvinyl chlorides.
- These thermoplastic resins may be used alone or in combination of two or more.
- an olefin-based thermoplastic resin is preferable because it is excellent in printability and embossing suitability of the pattern layer and is inexpensive.
- the transparent resin layer 1 may have a two-layer structure (having a transparent resin layer 1a and a transparent resin layer 1b).
- each of the transparent resin layers 1 may be laminated via a transparent adhesive layer described later. Further, the adjacent transparent resin layers 1 may be continuously laminated by a thermal laminating method.
- a thermal laminating method a known method such as a melt coextrusion method using a T-die can be used.
- the thickness of the transparent resin layer 1 is preferably 20 ⁇ m or more and 300 ⁇ m or less, more preferably 40 ⁇ m or more and 200 ⁇ m or less, and further preferably 50 ⁇ m or more and 150 ⁇ m or less.
- the scratch resistance and abrasion resistance of the decorative board using the transparent resin film 10 are further improved.
- the upper limit of the thickness of the transparent resin layer exceeds the above range, the sharpness of the decorative board using the transparent resin film 10 (meaning the visibility of the pattern layer described later) may decrease.
- the transparent resin layer 1 may be colored.
- a colorant may be added to the thermoplastic resin.
- the colorant pigments or dyes used in the pattern layer described later can be used.
- the transparent resin layer 1 and / or the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber.
- a case where the transparent resin layer 1 contains a triazine-based ultraviolet absorber will be described.
- triazine-based ultraviolet absorber examples 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-ethylhexyl) Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, N, N', N''-tri (m-tolyl) -1,3,5-triazine-2,4 6-
- the transparent resin layer 1 has a structure of at least two layers, from the viewpoint of preventing yellowing due to electron beam radiation when forming the transparent surface protective layer 2 described later while imparting weather resistance, with the pattern layer described later. From the viewpoint of adhesion, it is preferable that the transparent resin layer 1 (for example, in the case of a two-layer structure, the transparent resin layer 1a) on the side having the transparent surface protective layer 2 contains the triazine-based ultraviolet absorber.
- the content of the triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 3% by mass or less, preferably 0.2% by mass or more and 1% by mass or less, based on the mass of the transparent resin layer 1. More preferably, 0.5% by mass or less is further preferable. If the content of the triazine-based ultraviolet absorber in the transparent resin layer 1 is less than 0.1% by mass, it may not be possible to impart weather resistance, and if it exceeds 3% by mass, the transparency of the film becomes poor. The design of the decorative board may be impaired, or the adhesion to the pattern layer described later may not be sufficiently obtained, resulting in a decrease in processability.
- the transparent resin layer 1 is preferably 0.1% by mass or more and 3% by mass or less based on the mass of the layer containing the triazine-based ultraviolet absorber.
- each of the two or more layers contains the above-mentioned triazine-based ultraviolet absorber from the viewpoint of preferably suppressing yellowing during production.
- the content of the layer is more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
- the layer closer to the transparent surface protective layer 2 is more than the layer far from the transparent surface protective layer 2 from the viewpoint of imparting weather resistance. It is preferable that the content of the absorbent is high.
- the transparent resin layer 1 and / or the transparent surface protective layer 2 preferably contains a flame retardant.
- Flame retardants reduce flammability by forming chars during combustion and capturing radicals in combustion gas.
- a case where the transparent resin layer 1 contains a flame retardant will be described.
- 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, from the group consisting of phosphinic acid metal salt-based flame retardants, phosphazen-based flame retardants, and NOR-type hindered amine-based flame retardants, in terms 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.
- At least one selected has the property of trapping radicals generated from organic substances during combustion and making it difficult to continue combustion, and in the horizontal flammability test, metal phosphinate in terms of the effect of suppressing the spread of combustion. It is preferable to contain at least one selected from the group consisting of a salt-based flame retardant and a phosphazen-based flame retardant, which has the effect of reducing the calorific value in the heat generation test of ISO5660-1 and can also impart weather resistance. Therefore, NOR type hindered amine flame retardants are 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.
- phosphazene-based flame retardant examples include phenoxyphosphazene and (poly) triloxyphosphazene (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.
- phenoxyphosphazene and (poly) triloxyphosphazene eg, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,
- Aryloxyphosphazene and (poly) phenoxytriloxyphosphazene eg, phenoxyo-tolyloxyphosphazene, phenoxym-tolyloxyphosphazene, phenoxyp-tolyloxyphosphazene, phenoxyo, m-tolyloxyphosphazene, phenoxyo, p- Circular and /
- 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-.
- 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.
- 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.
- 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 transparent resin layer 1 has at least two layers, from the viewpoint of improving flame retardancy, a layer closer to the transparent surface protective layer 2 (for example, in the case of a two-layer structure, the transparent resin layer 1a) is the flame retardant. Is preferably contained.
- the content of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, based on the mass of the transparent resin layer 1.
- the content of the flame retardant is preferably 20% by mass or less, more preferably 15% by mass or less, based on the mass of the transparent resin layer 1.
- the transparent resin layer 1 preferably contains a filler.
- the filler is not particularly limited as long as it does not impair the transparency of the transparent resin layer 1, and is an average below the wavelength of visible light in that the sharpness of the decorative plate using the transparent resin film 10 is further improved.
- a filler showing a particle size is preferable.
- the filler include inorganic fillers such as silica, calcium carbonate, talc, and clay.
- the filler is preferably contained in the same layer as the layer containing the flame retardant. That is, when the transparent resin layer 1 has a one-layer structure and contains the flame retardant, it is preferable that the transparent resin layer 1 contains the filler. Further, when the transparent resin layer 1 has at least two layers and one of the layers contains the flame retardant, it is preferable that the layer containing the flame retardant contains the filler.
- the filler contains an inorganic filler having a polar group on the surface.
- the layer containing the flame retardant contains an inorganic filler having a polar group on the surface, the flame retardancy of the transparent resin film 10 is further improved, and the decorative plate using the transparent resin film 10 is sharp.
- the sex is further improved. 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.
- a hydrophilic inorganic filler can be used as the inorganic filler having a polar group on the surface.
- an inorganic filler having a hydroxyl group such as a silanol group on the surface can be used, and more specifically, hydrophilic silica is used. be able to.
- the silica used as the filler is preferably silica having a small average particle size from the viewpoint of further improving the sharpness of the decorative plate using the transparent resin film 10, and more preferably fumed silica obtained by a combustion method. Hydrophilic fumed silica is more preferred.
- 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 1 by adding the filler 1 The decrease in transparency of the transparent resin film 10 is further suppressed, the dispersibility of the flame retardant is further improved, the flame retardancy of the transparent resin film 10 and the sharpness of the decorative board using the transparent resin film 10 are further improved. Further improve. 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 10 is improved, and the content of the flame retardant can be reduced.
- the BET specific surface area is the BET specific surface area measured by the nitrogen adsorption method by the measuring method based on DIN66131.
- 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.
- the content of the filler in the layer containing the flame retardant is the content of the flame retardant in the layer containing the flame retardant in the transparent resin layer 1.
- the amount is 100 parts by mass, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 200 parts by mass or more.
- the lower limit of the content of the filler in the layer containing the flame retardant is within the above range, the sharpness of the decorative board using the transparent resin film 10 is further improved.
- the content of the filler in the layer containing the flame retardant 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 1 may be 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.
- 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.
- the transparent resin film 10 of the present invention has a transparent surface protective layer 2.
- the transparent surface protective layer 2 is a layer that imparts surface physical properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance.
- the transparent surface protective layer 2 is made of an ionizing radiation curable resin. Since the transparent surface protective layer 2 is made of an ionizing radiation curable resin, high surface hardness can be imparted.
- the ionizing radiation curable resin includes, for example, an oligomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule (hereinafter, also includes so-called prepolymer, macromonomer and the like) and / or a radical in the molecule.
- Monomers having a polymerizable unsaturated bond or a cationically polymerizable functional group are preferably used.
- 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.
- the oligomer or monomer examples 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.
- the said (meth) acryloyl group means an acryloyl group or a methacryloyl group.
- oligomers 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.
- molecular weight a molecular weight of about 2.5 to 100,000 is usually used.
- a polyfunctional monomer is preferable, and a polyfunctional (meth) acrylate is more preferable.
- 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.
- the polyfunctional monomer means a monomer having a plurality of radically polymerizable unsaturated groups.
- the transparent surface protective layer 2 can be obtained by curing the ionizing radiation curable resin composition made of the ionizing radiation curable resin.
- the ionizing radiation curable resin composition may contain a photopolymerization initiator.
- acetophenones, benzophenones, thioxanthones, benzoins, and benzoin methyl ethers are used alone or in combination as the photopolymerization initiator. Can be used.
- the transparent resin layer 1 and / or the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber. From the viewpoint of yellowing as described above while imparting weather resistance, it is preferable that the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber, and the transparent resin layer 1 and the transparent surface protective layer 2 are triazine. It is more preferable to contain a system UV absorber.
- a case where the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber will be described.
- the content of the triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 3% by mass or less based on the mass of the transparent surface protective layer 2. If the content of the triazine-based ultraviolet absorber in the transparent surface protective layer 2 is less than 0.1% by mass, weather resistance may not be imparted, and if it exceeds 3% by mass, the transparency of the film is impaired. The design of the decorative board may be deteriorated, or the adhesiveness with the transparent resin layer 1 may not be sufficiently obtained, so that the processability may be deteriorated.
- the transparent resin layer 1 and the transparent surface protective layer 2 more preferably contain a flame retardant from the viewpoint of more preferably improving the flame retardancy.
- the total mass of the transparent surface protective layer 2 is 100% by mass, and the lower limit of the content of the flame retardant is preferably 3% by mass and 4.4% by mass. % Is more preferable, and the upper limit of the content of the flame retardant is preferably 20% by mass, more preferably 15% by mass.
- the transparent surface protective layer 2 may contain the above-mentioned flame retardant. Since the transparent surface protective layer 2 contains a flame retardant, char formation, radical scavenging ability in combustion gas, and the like are exhibited against heat applied from the surface during combustion, so that flammability can be reduced. .. Regarding the content of the flame retardant in the transparent surface protective layer 2, the total mass of the transparent surface protective layer 2 is 100% by mass, and the lower limit of the content of the flame retardant is preferably 3% by mass and 4.4% by mass. % Is more preferable, and the upper limit of the content of the flame retardant is preferably 20% by mass, more preferably 15% by mass.
- the transparent surface protective layer 2 preferably contains the flame retardant and the filler from the viewpoint of improving the flame retardancy while maintaining the sharpness of the decorative board using the transparent resin film 10.
- the filler those described in the transparent resin layer 1 can be appropriately selected and used, preferably silica, and more preferably fumed silica in consideration of the dispersibility of the flame retardant.
- the silicas hydrophilic fumed silica is more preferable.
- the amount of the filler added is about 1 to 80 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.
- the transparent surface protective layer 2 may contain additives other than the above-mentioned filler.
- additives include antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, deodorants, antibacterial agents, antiviral agents, antiallergen agents, antifungal agents, antiallergen agents and the like. Be done.
- the transparent surface protective layer 2 preferably contains at least one of an antibacterial agent, an antiviral agent, and an antiallergen agent, if necessary.
- the transparent resin film 10 can be imparted with antibacterial and antiviral properties. Further, when the transparent surface protective layer 2 contains an anti-allergen agent, the transparent resin film 10 can be imparted with anti-allergen properties.
- the antibacterial agents and antiviral agents can be generally classified into organic and inorganic agents.
- 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.
- 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.
- benzimidazole compounds or anionic compounds that maintain the particle shape are preferably used.
- the above-mentioned “maintaining the particle shape” means that the transparent surface protective layer 2 exists in the state of particles without being dissolved in the composition (curable resin composition before curing) that becomes the curable resin. Therefore, in the process of forming the transparent surface protective layer 2, the particles of the benzimidazole compound or the particles of the anionic compound are likely to emerge, and the particles of the benzimidazole compound are on the outermost surface side of the transparent surface protective layer 2. Alternatively, the particles of the anionic compound can be easily unevenly distributed.
- the antibacterial agent and antiviral necessary for obtaining predetermined antibacterial and antiviral properties are obtained. Since the amount of the virus agent added can be suppressed, it is possible to easily suppress the decrease in scratch resistance of the transparent surface protective layer 2.
- 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.
- 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.
- only influenza virus which is a non-enveloped virus
- 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.
- 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 ⁇ m, 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.
- the color changes depending on the transparent surface protective layer 2 (when the added paint is discolored by heat or light, or when it is transparent.
- the color may change due to heat or light after the surface protective layer 2 is formed), but in this case, it can be improved by adding an ultraviolet inhibitor, a light stabilizer, or the like in a timely manner.
- an ultraviolet inhibitor 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.
- a material that supports a 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.
- 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.
- 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.
- water-insoluble polymer containing a phenolic hydroxyl group examples 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.
- 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.
- anionic phenolic material examples include tannin, tannic acid / sulphate, phenylsulfonic acid formaldehyde resin, noboratc type resin sulfone compound, noboratc 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 ⁇ m 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.
- the thickness of the transparent surface protective layer 2 is not particularly limited, but a preferable lower limit is 0.1 ⁇ m, a preferable upper limit is 50 ⁇ m, a more preferable lower limit is 1 ⁇ m, and a more preferable upper limit is 30 ⁇ m. If the thickness of the transparent surface protective layer 2 is less than 0.1 ⁇ m, sufficient durability (scratch resistance, stain resistance, weather resistance, etc.) may not be imparted, and if it exceeds 50 ⁇ m, the present invention The transmittance of the transparent resin film 10 of the above may decrease, and the visibility of the pattern in the pattern layer may decrease.
- additives may be added to the transparent surface protective layer 2 as needed.
- 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, light stabilizers such as hindered amine radical traps, glosses such as silica, acrylic beads and mica, tactile adjusters, dyes, pigments, etc. Coloring agent, etc.
- the transparent resin film 10 of the present invention preferably has an adhesive primer layer 3 on the side opposite to the transparent surface protective layer 2 side of the transparent resin layer 1.
- an adhesive primer layer 3 By having the adhesive primer layer 3, it is possible to preferably impart adhesion to the pattern layer laminated on one of the base materials.
- the adhesive primer layer preferably contains a binder resin.
- the binder resin include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose resin, polyester resin, vinyl chloride-vinyl acetate copolymer and the like.
- the urethane resin is preferable from the viewpoint of adhesiveness to the surface protective layer and efficiency during production.
- the thickness of the adhesive primer layer 3 is preferably 0.5 ⁇ m or more and 10 ⁇ m or less. If it is 0.5 ⁇ m or more, the adhesion between the transparent resin film 10 and the base material on which the pattern layer described later is laminated can be suitably secured, and if it is 10 ⁇ m or less, the transparent resin film 10 does not become too thick. Sufficient transparency can be obtained, and the design of the decorative board can be preferably ensured.
- the thickness of the adhesive primer layer 3 is more preferably 0.8 ⁇ m or more and 6 ⁇ m or less.
- the adhesive primer layer 3 may contain inorganic fine particles such as silica, if necessary.
- a known adhesive may be used as the transparent adhesive layer.
- a known adhesive may be used as the transparent adhesive layer.
- These adhesives may be used alone or in combination of two or more, or may be a two-component curable type, a moisture-curable type, an ionizing radiation curable type, or an adhesive (tack agent).
- the thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 ⁇ m, more preferably about 1 to 5 ⁇ m.
- a primer layer for a transparent surface protective layer between the transparent surface protective layer 2 and the transparent resin layer 1.
- the primer layer for the transparent surface protective layer may contain the ultraviolet absorber.
- the same primer layer as the above-mentioned adhesive primer layer can be preferably used.
- the transparent resin film 10 may have an uneven shape on the side where the pattern layers described later are laminated.
- the Rzmax defined by JIS B 0601 (2001) of the concavo-convex shape is preferably 80 ⁇ m or less.
- the Rzmax defined by JIS B 0601 (2001) having an uneven shape on the side where the pattern layers are laminated exceeds 80 ⁇ m, air bubbles are likely to enter between the pattern layer and the transparent resin film 10.
- the design of the decorative board of the present invention may be deteriorated.
- the Rzmax defined by JIS B 0601 (2001) having an uneven shape on the side where the pattern layers are laminated is more preferably 60 ⁇ m or less, further preferably 55 ⁇ m or less, and particularly preferably 50 ⁇ m or less. preferable.
- the lower limit of Rzmax defined by JIS B 0601 (2001) having an uneven shape on the side where the pattern layers are laminated is, for example, 15 ⁇ m.
- the Rzmax can be obtained by measuring with a surface roughness measuring instrument (“SURFCOM-FLEX-50A”, manufactured by Tokyo Seimitsu Co., Ltd.) under the following conditions.
- 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.
- the heat embossing include a method of embossing with a well-known single-wafer or rotary embossing machine.
- the embossed pattern include sand grain, hairline, satin finish, wood grain conduit groove, stone plate surface unevenness, cloth surface texture, and perennial groove.
- 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 concave-convex shape when the concave-convex shape is formed on the side where the pattern layers are laminated, the concave-convex shape may be formed on both sides of the transparent resin film 10 by the above method, or one of the transparent resin films 10 may be formed. A concave-convex shape may be formed on one side by the above method, and the concave-convex shape on the other side may be formed by following the concave-convex shape formed on one side.
- the transparent resin film 10 preferably has an uneven shape on the side opposite to the side laminated on the pattern layer described later.
- the uneven shape on the side opposite to the side laminated on the pattern layer, which will be described later, is appropriately adjusted so that the center line average roughness Ra defined in JIS B 0601 (1982) is within the range of 1 ⁇ m or more and 30 ⁇ m or less. It is preferable to do so.
- the thickness of the concave-convex concave portion on the side opposite to the side laminated on the pattern layer is preferably 80 ⁇ m or more. If the thickness of the concave-convex concave portion of the transparent resin film 10 is less than 80 ⁇ m, it may not be possible to impart sufficient durability (wear resistance, scratch resistance) to the decorative board.
- the above-mentioned “concave and convex concave portion” will be described.
- the “concave-convex-shaped recess” refers to the thinnest portion of the thickness of the transparent resin film 10, and as shown in FIG. 3, the deepest concave-convex-shaped recess of the transparent surface protective layer 2 is used.
- the length from the bottom of the concave-convex-shaped deepest recess on the transparent surface protection layer 2 side of the transparent resin layer 1 to the opposite surface is the "thickness of the concave-convex-shaped recess".
- a protrusion is generated on the surface on the opposite side corresponding to the deepest concave portion having the concave-convex shape on the surface protective layer 2 side, but the concave-convex shape on the transparent surface protective layer 2 side of the transparent resin layer 1
- the length from the bottom of the deepest recess to the surface on the opposite side where such a protrusion exists is the "thickness of the concave-convex recess".
- the upper limit of the thickness of the concave-convex concave portion of the transparent resin film 10 is not particularly limited, but is preferably 500 ⁇ m, for example. As shown in FIG. 3, the total thickness of the transparent resin film 10 is the length from the surface having the transparent surface protective layer 2 to the surface on the opposite side.
- the preferred lower limit of the total thickness is 100 ⁇ m, the preferred upper limit is 500 ⁇ m, the more preferred lower limit is 140 ⁇ m, and the more preferred upper limit is 460 ⁇ m.
- the various additives inorganic filler added to the primer layer and the surface protection layer, etc.
- 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.
- vesicle treatment method examples include a Bangham method, an extrusion method, a hydration method, a reverse phase evaporation method, and a freeze-thaw method.
- a 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.
- 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.
- 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.
- 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. , Ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.
- a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.
- nonionic surfactant examples 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, ⁇ -cholestanol, ⁇ -cholestanol, cholestane, desmosterol (5,24-cholestadien-3 ⁇ -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.
- the outer membrane 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.
- the method for producing the transparent resin film 10 of the present invention is a preparatory step of preparing a transparent resin layer containing a triazine-based ultraviolet absorber, and a coating in which an ionizing radiation curable resin is applied to one surface of the transparent resin layer. It is characterized by having a step and an irradiation step of irradiating the ionizing radiation curable resin with an electron beam.
- the preparatory step is preferably a step of preparing a thermoplastic resin and laminating a thermoplastic resin containing a triazine-based ultraviolet absorber on one of the thermoplastic resins to obtain a transparent resin layer.
- a transparent resin layer By containing the triazine-based ultraviolet absorber in the transparent resin layer 1a on the side of the transparent resin film 10 having the transparent surface protective layer 2, yellowing due to irradiation with an electron beam in the irradiation step is more preferably suppressed.
- the weather resistance can be preferably imparted, and the adhesion to the pattern layer described later can be more preferably imparted.
- the ionizing radiation curable resin preferably contains a triazine-based ultraviolet absorber.
- the transparent surface protective layer 2 can be formed by applying an ionizing radiation curable resin containing a triazine-based ultraviolet absorber.
- the transparent surface protective layer 2 of the transparent resin film 10 contains a triazine-based ultraviolet absorber, the above-mentioned yellowing can be suppressed and weather resistance can be preferably imparted.
- Examples of the coating step include a method of applying a solution of an ionizing radiation curable resin composition by a coating method such as a gravure coating method or a roll coating method.
- the coating amount of the ionizing radiation curable resin in the coating step may be controlled so as to be within a preferable range of the thickness of the transparent surface protective layer 2 described above.
- Examples of the electron beam source in the irradiation step include Cockcroft-Walton type, Van de Graaff type, resonance transformer type, insulated core transformer type, and various electron beam accelerators such as linear type, dynamistron type, and high frequency type. Those capable of irradiating electrons having an energy of 70 to 1000 keV can be appropriately selected and used.
- the irradiation amount of ionizing radiation is preferably, for example, about 1 to 10 Mrad. Further, ultraviolet rays can also be used.
- 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 may be used to irradiate in the wavelength range of 190 to 380 nm. ..
- Examples of the method of laminating each layer of the transparent resin film 10 include a method of laminating via the transparent adhesive layer, an adhesive primer layer and the like, a method of laminating by a thermal laminating method, and the like.
- a known method such as a melt coextrusion method using a T-die can be used.
- FIG. 5 is a cross-sectional view schematically showing an example of a decorative board.
- the decorative board 20 has a pattern layer 12 laminated on one of the base materials 11, and the pattern layer 12 and the transparent resin film 10 of the present invention are laminated via an adhesive layer 13. Has.
- each configuration will be described.
- the base material 11 is not particularly limited, but is appropriately determined according to the use of the decorative board, for example.
- the material constituting the base material 11 is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, and metal materials. Among them, as the material constituting the base material, a resin material or a wood material having rigidity and lightness is preferable. Further, these composite materials may be used.
- the resin material for example, it is preferable to contain a thermoplastic resin.
- thermoplastic resin examples 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.
- Polyolefin resin such as based resin, polyester resin such as polyethylene terephthalate resin (PET resin), acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin, etc.
- thermoplastic resin 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 a mixed resin thereof.
- 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 a mixed resin thereof.
- 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 a mixed resin thereof.
- polyolefin resins acrylonitrile-butadiene-styrene copolymer resins, polyvinyl chloride resins
- wood-based material examples 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.
- the base material 11 may contain an inorganic compound. By containing the inorganic compound, the coefficient of linear expansion of the base material can be reduced, and as a result, the water resistance of the transparent resin film 10 can be improved.
- the base material 11 is, if necessary, a colorant (pigment or dye), a filler such as wood powder or calcium carbonate, a matting agent such as silica, a foaming agent, a flame retardant, a lubricant such as talc, and an antistatic agent.
- Various additives such as an agent, an antioxidant, an ultraviolet absorber, and a light stabilizer may be contained.
- 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.
- the base material 11 may have a hollow structure, or a slit groove or a through hole may be provided in a part of the base material.
- the size of the base material 11 is not particularly limited, and can be appropriately determined depending on the use of the decorative board.
- the thickness of the base material 11 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.
- the base material 11 includes a substantially plate shape other than a flat plate, and includes a base material 11 having irregularities and curved surfaces. When the base material 11 is as thin as 1 mm or less, an adherend described later may be provided on the back surface of the base material 11.
- the pattern layer 12 is a layer that imparts decorativeness to the decorative board, and may be, for example, a uniformly colored concealing layer (solid printing layer), or various patterns may be printed using ink and a printing machine. It may be a pattern layer formed by the above, or it may be a layer in which a concealing layer and a pattern layer are combined (hereinafter, a pattern layer).
- 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.
- 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 brickwork Patterns, etc., or a combination of these, such as parquet, patchwork, letters, symbols, abstract patterns, flower patterns, landscapes, and characters, can be added to the veneer.
- 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.
- 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.
- 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, yellow lead, titanium yellow, petal handle, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments, quinacridone red, and isoindolinone.
- Organic pigments such as yellow and phthalocyanine blue, metal pigments consisting of scaly foil pieces such as dyes, aluminum and brass, titanium dioxide-coated mica, pearl gloss pigments consisting of scaly foil pieces such as basic lead carbonate, etc. Is preferably mentioned.
- the thickness of the pattern layer 12 is not particularly limited, and is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more and 600 ⁇ m or less, for example. When the thickness of the pattern layer 12 is within the above range, an excellent design can be imparted to the decorative board, and concealment can be imparted.
- the decorative board 20 may further have an adhesive layer, a primer layer, a backer layer, and the like, if necessary.
- the adherend may be provided on the back side of the adhesive layer, the primer layer, the backer layer, and the like.
- the adhesive layer and the primer layer the same ones as those described in the transparent resin film 10 can be preferably used.
- backer layer examples include a resin backer layer such as a synthetic resin backer layer and a foamed resin backer layer, a wood-based backer layer such as cork, and a non-woven fabric-based backer layer. It is preferable to have it on the side opposite to the side to be laminated). When the base material 11 has the backer layer, the scratch resistance and impact resistance of the decorative board can be further improved.
- Examples of the resin constituting the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and highly heat-resistant polyalkylene terephthalate [for example, a part of ethylene glycol.
- the synthetic resin backer layer may contain hollow beads.
- the type, particle size, content, etc. of the hollow beads those described in JP-A-2014-188941 can be applied.
- the backer layer may contain a flame retardant.
- a flame retardant those described in the transparent resin film 10 can be appropriately selected and used.
- the thickness of the synthetic resin backer layer is not particularly limited, but is preferably 100 to 600 ⁇ m, more preferably 150 to 450 ⁇ m, for example.
- Examples of the method for forming the synthetic resin backer layer include calendar molding, extrusion molding of molten resin, and the like. Of these, extrusion molding of molten resin is preferable, and for example, extrusion molding using a T-die is more preferable.
- the foamed resin backer layer may be further lower than the synthetic resin backer layer (on the side opposite to the side having the uneven shape).
- the foamed resin backer layer those described in JP-A-2014-188941 can be applied.
- the adherend may be provided on the back surface (the side opposite to the side having the transparent resin film 10).
- the material of the adherend is, for example, a wood board such as a single wood board, a wood plywood, a particle board, an MDF (medium density fiberboard), an HDF (high density fiberboard); Cement boards such as calcium silicate board, asbestos slate board, lightweight foamed concrete board, hollow extruded cement board; fiber cement board such as pulp cement board, asbestos cement board, wood piece cement board; pottery, porcelain, earthenware, glass, amber, etc. Ceramic plates; metal plates such as iron plates, zinc-plated steel plates, polyvinyl chloride sol-coated steel plates, aluminum plates, and copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, polycarbonate plates, and polyvinyl chloride resin plates.
- Thermocurable resin plates such as phenol resin plate, urea resin plate, unsaturated polyester resin plate, polyurethane resin plate, epoxy resin plate, melamine resin plate; phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin , So-called FRP board in which a resin such as melamine resin or diallyl phthalate resin is impregnated and cured in a glass fiber non-woven fabric, cloth, paper, or other various fibrous base materials and cured, and these can be used alone. Often, it may be used as a composite substrate in which two or more of these are laminated.
- the thickness of the adherend is not particularly limited.
- 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.
- colorants pigments or dyes
- fillers such as wood powder and calcium carbonate
- matting agents such as silica
- foaming agents such as flame retardants, and talc.
- talc Various additives such as lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be contained.
- the method for producing a decorative board of the present invention is a method for manufacturing a decorative board including a base material on which a pattern layer is laminated and the transparent resin film of the present invention in this order, wherein the pattern layer of the transparent resin film is It is characterized by having a step of forming an adhesive layer on the surface on the side to be laminated and a step of adhering the transparent resin film and the pattern layer via the adhesive layer.
- the transparent resin film 10 when the uneven shape on the opposite side surface of the pattern layer 12 is formed, embossing or the like is performed to form the uneven shape, but the embossed surface side is formed. Following the uneven shape, a slight uneven shape is formed on the surface (base layer side) opposite to the embossed surface. In such a case, so-called air shavings, in which air enters the uneven shape on the side where the pattern layer formed on the transparent resin film 10 is laminated, may occur, and the design may be deteriorated.
- the step of forming the adhesive layer 13 on the surface of the transparent resin film 10 on the side to be laminated on the pattern layer 12 since the step of forming the adhesive layer 13 on the surface of the transparent resin film 10 on the side to be laminated on the pattern layer 12, the unevenness on the side to be laminated on the pattern layer 12 is provided.
- the adhesive layer 13 can also be inserted into the concave portion of the shape, the occurrence of the above-mentioned air shavings can be prevented, and the deterioration of the design can be suppressed.
- the thickness of the decorative board 20 is not particularly limited, and for example, it is preferably 0.05 mm or more, and more preferably 1 mm or more and 50 mm or less.
- Example 1 A transparent polypropylene film (thickness 60 ⁇ m, also referred to as a transparent resin layer b) is prepared, and a two-component curable urethane resin adhesive primer is applied to one side of the transparent resin layer b, and the adhesive primer layer (also referred to as a transparent resin layer b) is applied. A thickness of 2 ⁇ m) was formed. Next, a transparent polypropylene resin (thickness 100 ⁇ m, also referred to as a transparent resin layer a) containing a triazine-based ultraviolet absorber is extruded and heat-laminated on one side (opposite side of the adhesive primer layer) of the transparent resin layer b. Laminated by the method.
- a primer agent thickness 2 ⁇ m
- a two-component curable urethane acrylic copolymer resin was applied to form a primer layer for a surface protective layer.
- an ionizing radiation curable resin coating amount: 15 ⁇ m
- an acceleration voltage of 165 keV is applied using an electron irradiation device.
- a transparent surface protective layer was formed by irradiating an electron beam under the condition of 30 KGy.
- the transparent surface protective layer side is heated by an infrared non-contact heater to soften the transparent resin layer a and the transparent resin layer b, and then immediately embossing by heat pressure is performed to shape the uneven shape.
- Table 1 shows the thickness of the transparent resin layers (a and b) and the content of the ultraviolet absorber in the transparent surface protective layer.
- the thickness of the concave-convex concave portion on the side opposite to the side laminated on the pattern layer of the transparent resin film was 100 ⁇ m.
- the uneven shape on the side where the pattern layer of the transparent resin film is laminated has an Rzmax of 40 ⁇ m defined by JIS B 0601 (2001).
- the above-mentioned "thickness of the concave-convex-shaped concave portion" and Rzmax were measured by using the method described in the present specification.
- Example 2 In the transparent resin layer a laminated by the extrusion heat laminating method, a transparent resin film was produced in the same manner as in Example 1 except that the extrusion thickness was 60 ⁇ m.
- the thickness of the concave-convex concave portion of the obtained transparent resin film and the Rzmax defined by JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated are as shown in Table 3.
- Example 3 A transparent resin film was produced in the same manner as in Example 1 except that the content of the ultraviolet absorber was changed as shown in Table 1.
- Comparative Example 2 A transparent resin film was produced in the same manner as in Comparative Example 1 except that the content of the ultraviolet absorber was changed as shown in Table 1.
- Example 4 In the transparent resin layer a laminated by the extrusion heat laminating method, the same as in Example 1 except that 10 parts of a phosphinic acid metal salt-based flame retardant (manufactured by Pekoflam STC Achroma) was added to 100 parts of the transparent polypropylene resin. A transparent resin film was produced in the same manner. The content of the flame retardant was 5.7% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.
- a phosphinic acid metal salt-based flame retardant manufactured by Pekoflam STC Achroma
- Example 5 A transparent resin film was produced in the same manner as in Example 4 except that the flame retardant was changed to a phosphazene-based flame retardant (Ravitor FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd.). The content of the flame retardant was 5.7% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.
- Example 6 In the transparent resin layer a, the transparent resin film is the same as in Example 1 except that 30 parts of a phosphinic acid metal salt-based flame retardant (manufactured by Pekoflam STC Arcroma) is added to 100 parts of the transparent polypropylene resin. Was produced. The content of the flame retardant was 14.4% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.
- a phosphinic acid metal salt-based flame retardant manufactured by Pekoflam STC Arcroma
- Example 7 A transparent resin film was produced in the same manner as in Example 1 except that embossing was performed with a deep embossing plate different from that in Example 1.
- the thickness of the concave-convex concave portion of the obtained transparent resin film and the Rzmax defined by JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated are as shown in Table 3.
- Example 8 A transparent resin film was produced in the same manner as in Example 2 except that the same deep embossed plate as in Example 7 was used.
- the thickness of the concave-convex concave portion of the obtained transparent resin film and the Rzmax defined by JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated are as shown in Table 3.
- Example 9 Transparent as in Example 1 except that 3 parts by mass of a phosphoric acid-based glass silver-supporting compound (manufactured by Koa Glass Co., Ltd./PG-711) was added to 100 parts by weight of the ionizing radiation curable resin. A sex resin film was produced.
- a phosphoric acid-based glass silver-supporting compound manufactured by Koa Glass Co., Ltd./PG-711
- Example 10 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 was produced in the same manner as in Example 1 except that EXP20530B ”) was blended in a solid content ratio of 23% by mass.
- the film in the state before the ionizing radiation curable resin was applied (the state in which the transparent resin layers (a and b) and the adhesive primer layer were formed) was used as the test film. ..
- the test film was placed on a standard white plate, and L 1 * , a 1 * , and b 1 * were measured by the following methods.
- the test film was irradiated with an electron beam using an electron irradiation device under the conditions of an acceleration voltage of 165 keV and 30 KGy.
- L * , a * , b * are standardized by the CIE (Commission Internationale de l'Eclairage) and are "L * , a * , b *" in the color system adopted in JIS Z8781-4: 2013. * ”Is meant.
- a decorative board was produced by laminating the obtained transparent resin film so that the adhesive primer layer side was in contact with the decorative surface (pattern layer) of the directly printed wood substrate.
- the transparent resin film obtained in the examples can suppress yellowing even when irradiated with an electron beam when forming the transparent surface protective layer, and can prevent deterioration of design. Further, it was confirmed that the transparent resin layer was excellent in flame retardancy in Examples 4 to 6 containing a flame retardant. Further, Examples 1, 2 and 8 in which the thickness of the concave-convex concave portion of the transparent resin film is 80 ⁇ m or more is also excellent in wear resistance, and the Rzmax of the concave-convex shape on the side where the pattern layer is laminated is 80 ⁇ m. Examples 1, 2 and 7 described below were excellent in design, and Example 1 in which Rzmax was 50 ⁇ m or less was particularly excellent in design.
- Example 9 in which the transparent surface protective layer contained an antibacterial agent or an antiviral agent, it was confirmed that the transparent surface protective layer had an antibacterial agent or an antiviral property, and in Example 10 in which the transparent surface protective layer contained an antiallergen agent, it was confirmed. It was confirmed to have antiallergenicity.
- the transparent resin film contains a benzotriazole-based ultraviolet absorber, yellowing occurs due to irradiation with an electron beam when forming the transparent surface protective layer.
- the present invention has an excellent design property due to having an uneven shape, and while imparting weather resistance, it suppresses yellowing even when irradiated with an electron beam and prevents deterioration of the design property.
- a transparent resin film that can be obtained can be obtained.
- the decorative board of the present invention using the transparent resin film of the present invention is, for example, interior materials of buildings such as walls, ceilings and floors; fittings such as window frames, doors and handrails; furniture; home appliances, OA. Housing for equipment, etc .; Can be suitably used as an exterior material for entrance doors, etc.
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Abstract
Description
透明性樹脂フィルムは、耐候性を向上させるために、透明性樹脂フィルムを構成する層に、耐候剤を添加することがある。
しかしながら、特許文献1では、印刷面を光から保護して退色を防止することは開示されているが、オーバーラミネート用フィルムの表面に凹凸形状を形成することは考慮されておらず、近年要求される意匠性を有するものではなかった。
また、本発明の透明性樹脂フィルムは、上記絵柄層が積層される側に凹凸形状を有し、上記絵柄層が積層される側に凹凸形状のJIS B 0601(2001)で定義されるRzmaxが、80μm以下であることが好ましい。
また、上記透明性樹脂層の前記透明性表面保護層側と反対側に接着用プライマー層を有することが好ましい。
また、上記透明性樹脂層は、熱可塑性樹脂からなることが好ましい。
また、上記透明性樹脂層は、少なくとも2層構成であることが好ましい。
また、上記透明性樹脂層は、難燃剤を含有することが好ましい。
また、上記透明性表面保護層は、難燃剤を含有することが好ましい。
また、上記透明性樹脂層のうち上記難燃剤を含有する層は、充填剤を含有することが好ましい。
また、上記難燃剤は、ホスフィン酸金属塩系難燃剤、ホスファゼン系難燃剤及びNOR型ヒンダードアミン系難燃剤からなる群より選択される少なくとも1種であることが好ましい。
また、上記透明性表面保護層は、抗菌剤、抗ウイルス剤、及び、抗アレルゲン剤の少なくとも1種を含有することが好ましい。
また、上記透明性樹脂フィルムと絵柄層を備えた基材とが設けられた化粧板であることが好ましい。
本発明の透明性樹脂フィルムの製造方法は、トリアジン系紫外線吸収剤を含有する透明性樹脂層を準備する準備工程、上記透明性樹脂層の一方の面に、電離放射線硬化型樹脂を塗布する塗布工程、及び、上記電離放射線硬化型樹脂に電子線を照射する照射工程を有することを特徴とする。
上記準備工程は、熱可塑性樹脂を準備し、上記熱可塑性樹脂の一方にトリアジン系紫外線吸収剤を含有する熱可塑性樹脂を積層して、透明性樹脂層を得る工程であることが好ましい。
また、上記電離放射線硬化型樹脂は、トリアジン系紫外線吸収剤を含有することが好ましい。
本発明の化粧板の製造方法は、絵柄層が積層された基材と、本発明の透明性樹脂フィルムとをこの順に備える化粧板の製造方法であって、上記透明性樹脂フィルムの絵柄層が積層される側の面に接着剤層を形成する工程、及び、上記接着剤層を介して、上記透明性樹脂フィルムと上記絵柄層とを貼り合わせる工程を有することを特徴とする。
以下、本発明の透明性樹脂フィルムについて説明する。
なお、以下の記載において、「~」で表される数値範囲の下限上限は「以上以下」を意味する(例えば、α~βならば、α以上β以下である)。
本発明の透明性樹脂フィルム10は、少なくとも透明性樹脂層1と、透明性表面保護層2とがこの順に積層されており、透明性表面保護層2は、電離放射線硬化型樹脂からなり、透明性樹脂層1及び/又は透明性表面保護層2は、トリアジン系紫外線吸収剤を含有する。
本発明の透明性樹脂フィルム10において、透明性樹脂層1は、透明性樹脂層1aと、透明性樹脂層1bとを有する2層構成であることが好ましい。
また、透明性樹脂層1の透明性表面保護層2側と反対側に接着用プライマー層3を有することが好ましい。
以下、各構成について説明する。
本発明の透明性樹脂フィルム10は、透明性樹脂層1を有する。
これらの熱可塑性樹脂は単独で用いてもよいし、2種以上を混合して用いてもよい。
これらのなかでも、絵柄層の印刷適性及びエンボス加工適性に優れ、安価である点で、オレフィン系熱可塑性樹脂が好ましい。
また、隣り合う透明性樹脂層1同士が、熱ラミネート方式により連続して積層されていてもよい。
上記熱ラミネート方式としては、Tダイを用いた溶融共押出し法等の公知の方法を用いることができる。
透明性樹脂層の厚みの下限が上記範囲であることにより、透明性樹脂フィルム10を用いた化粧板の耐傷性及び耐摩耗性がより一層向上する。また、透明性樹脂層の厚みの上限が上記範囲を超えると、透明性樹脂フィルム10を用いた化粧板の鮮鋭性(後述する絵柄層の視認性を意味する)が低下することがある。
以下、透明性樹脂層1がトリアジン系紫外線吸収剤を含有する場合について説明する。
1種単独で又は2種以上を混合して用いることができる。
透明性樹脂層1における上記トリアジン系紫外線吸収剤の含有量が0.1質量%未満であると、耐候性を付与することもできないことがあり、3質量%を超えると、フィルムの透明性が損なわれ化粧板の意匠性が低下したり、後述する絵柄層との密着性が十分に得られず、加工適性が低下したりすることがある。
なお、透明性樹脂層1を2層以上有する場合においても、上記トリアジン系紫外線吸収剤を含有する層の質量を基準として、0.1質量%以上3質量%以下であることが好ましい。透明性樹脂層1を2層以上有する場合には、製造の際の黄変を好適に抑制する観点から、2層以上の層のそれぞれに上記トリアジン系紫外線吸収剤を含有することが好ましく、それぞれの層における含有量が1質量%以下がより好ましく、0.5質量%以下が更に好ましい。
また、透明性樹脂層1を2層以上有する場合、耐候性を好適に付与する観点から、透明性表面保護層2に近い層が、透明性表面保護層2から遠い層よりも上記トリアジン系紫外線吸収剤の含有量が多い方が好ましい。
難燃剤は、燃焼時のチャー形成や燃焼ガス中のラジカルの捕捉等により、燃焼性を低減させる。
以下、透明性樹脂層1が難燃剤を含有する場合について説明する。
なかでも、環境の観点もしくは添加量を抑えられ難燃剤を含有する層の透明性を維持できる点で、ホスフィン酸金属塩系難燃剤、ホスファゼン系難燃剤及びNOR型ヒンダードアミン系難燃剤からなる群より選択される少なくとも1種であることが好ましく、燃焼時に有機物から発生するラジカルをトラップし燃焼を継続し難くする性質を有し、水平燃焼性試験においては燃え広がりを抑制する効果の点でホスフィン酸金属塩系難燃剤、ホスファゼン系難燃剤からなる群から選択される少なくとも1種を含むことが好ましく、ISO5660-1の発熱性試験において発熱量を低下させる効果があり、耐候性を付与することもできることから、NOR型ヒンダードアミン系難燃剤が好ましい。
上記ホスフィン酸金属塩系難燃剤の市販品としては、クラリアントジャパン社製 商品名「EXOLITE OP-930」、「EXOLITE OP-935」、「EXOLITE OP-1230」、「EXOLITE OP-1240」、「EXOLITE OP-1312」等が挙げられる。
また、4,4’-スルホニルジフェニレン(ビスフェノールS残基)の架橋構造を有する化合物、2,2-(4,4’-ジフェニレン)イソプロピリデン基の架橋構造を有する化合物、4,4’-オキシジフェニレン基の架橋構造を有する化合物、4,4’-チオジフェニレン基の架橋構造を有する化合物等の、4,4’-ジフェニレン基の架橋構造を有する化合物等も挙げられる。
また、上記難燃剤の含有量は、透明性樹脂層1の質量を基準として、20質量%以下が好ましく、15質量%以下がより好ましい。
上記難燃剤の含有量の下限が上記範囲であることにより、透明性樹脂フィルム10の難燃性がより一層向上する。また、上記難燃剤の含有量の上限が上記範囲であることにより、透明性樹脂フィルム10の透明性がより一層維持される。
なお、透明性樹脂層1を2層以上有する場合は、上記難燃剤を含有する層の質量を基準として、3質量%以上が好ましく、4.4質量%以上がより好ましく、20質量%以下が好ましく、15質量%以下がより好ましい。
上記充填剤は、透明性樹脂層1の透明性を損なわなければ特に限定されず、透明性樹脂フィルム10を用いた化粧板の鮮鋭性がより一層向上する点で、可視光の波長以下の平均粒子径を示す充填剤が好ましい。
上記充填剤としては、例えば、シリカ、炭酸カルシウム、タルク、クレー等の無機フィラーが挙げられる。
すなわち、透明性樹脂層1が1層構成であり、上記難燃剤を含有する場合、透明性樹脂層1が上記充填剤を含有することが好ましい。また、透明性樹脂層1が少なくとも2層構成であり、そのうちの1層が上記難燃剤を含有する場合、上記難燃剤を含有する層が、上記充填剤を含有することが好ましい。
上記難燃剤を含有する層が、表面に極性基を有する無機フィラーを含有することにより、透明性樹脂フィルム10の難燃性がより一層向上し、透明性樹脂フィルム10を用いた化粧板の鮮鋭性がより一層向上する。これは、上記難燃剤の極性部が極性基を有する無機フィラーの表面の極性基に引き付けられ、表面に上記難燃剤が存在することにより、分散性が向上するためであると考えられる。
上記表面に極性基を有する無機フィラーとしては、親水性無機フィラーを用いることができ、例えば、表面にシラノール基等の水酸基を有する無機フィラーが挙げられ、より具体的には、親水性シリカを用いることができる。
上記充填剤として用いられるシリカは、透明性樹脂フィルム10を用いた化粧板の鮮鋭性がより一層向上する点から平均粒子径の小さいシリカが好ましく、燃焼法により得られるフュームドシリカがより好ましく、親水性フュームドシリカが更に好ましい。
上記充填剤のBET比表面積の下限が上記範囲であることにより、平均粒子径が小さく、親水性フュームドシリカの場合はシラノール量が増加するため、充填剤を添加することによる透明性樹脂層1の透明性の低下がより一層抑制され、且つ、上記難燃剤の分散性がより一層向上し、透明性樹脂フィルム10の難燃性及び透明性樹脂フィルム10を用いた化粧板の鮮鋭性がより一層向上する。また、充填剤のBET比表面積の下限が上記範囲であることにより、透明性樹脂フィルム10の難燃性が向上し、難燃剤の含有量を減少させることが可能となる。
上記難燃剤を含有する層中の充填剤の含有量の下限が上記範囲であることにより、透明性樹脂フィルム10を用いた化粧板の鮮鋭性がより一層向上する。また、上記難燃剤を含有する層中の充填剤の含有量は、25質量部以下が好ましく、20質量部以下がより好ましく、10質量部以下が更に好ましい。
本発明の透明性樹脂フィルム10は、透明性表面保護層2を有する。
透明性表面保護層2は、耐傷性、耐摩耗性、耐水性、耐汚染性等の表面物性を付与する層である。
透明性表面保護層2が電離放射線硬化型樹脂からなることにより、高い表面硬度を付与することができる。
なお、ここで電離放射線とは、分子を重合或いは架橋させ得るエネルギーを有する電磁波又は荷電粒子を意味し、通常は、電子線(EB)又は紫外線(UV)が一般的である。
上記多官能(メタ)アクリレートとしては、例えば、ジエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ビスフェノールAエチレンオキサイド変性ジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンエチレンオキサイドトリ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート{5官能(メタ)アクリレート}、ジペンタエリスリトールヘキサ(メタ)アクリレート{6官能(メタ)アクリレート}等が挙げられる。ここで、多官能モノマーとは、複数のラジカル重合性不飽和基を有するモノマーをいう。
なお、必要に応じ、上記電離放射線硬化型樹脂に加えて、単官能モノマーを本発明の目的に反しない範囲で適宜使用しても良い。
上記単官能モノマーとしては、例えば、メチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等が挙げられる。
上記電離放射線硬化型樹脂組成物は、光重合開始剤を含有しても良い。
上記電離放射線硬化型樹脂組成物がラジカル重合性不飽和基を有する樹脂系の場合、上記光重合開始剤として、アセトフェノン類、ベンゾフェノン類、チオキサントン類、ベンゾイン、ベンゾインメチルエーテル類を単独又は混合して用いることができる。
また、上記電離放射線硬化型樹脂組成物がカチオン重合性不飽和基を有する樹脂系の場合、上記光重合開始剤として、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、メタセロン化合物、ベンゾインスルホン酸エステル等を単独又は混合物として用いることができる。
なお、これらの光重合開始剤の添加量としては、電離放射線硬化型樹脂100質量部に対して0.1~10質量部程度である。
耐候性を付与しつつ、上述した黄変をする観点から、透明性表面保護層2がトリアジン系紫外線吸収剤を含有することが好ましく、透明性樹脂層1及び透明性表面保護層2が、トリアジン系紫外線吸収剤を含有することがより好ましい。
以下、透明性表面保護層2がトリアジン系紫外線吸収剤を含有する場合について説明する。
透明性表面保護層2における上記トリアジン系紫外線吸収剤の含有量が0.1質量%未満であると、耐候性を付与できないことがあり、3質量%を超えると、フィルムの透明性が損なわれ化粧板の意匠性が低下したり、透明性樹脂層1との密着性が十分に得られず、加工適性が低下したりすることがある。
透明性表面保護層2が難燃剤を含有することで、燃焼時に表面から加わる熱に対して、チャー形成や燃焼ガス中のラジカル捕捉能等が発現するために、燃焼性を低減することができる。
透明性表面保護層2における難燃剤の含有量は、透明性表面保護層2の質量の合計を100質量%として、上記難燃剤の含有量の下限は、3質量%が好ましく、4.4質量%がより好ましく、上記難燃剤の含有量の上限は、20質量%が好ましく、15質量%がより好ましい。
上記充填剤としては、透明性樹脂層1で記載したものを適宜選択して用いることができ、シリカであることが好ましく、難燃剤の分散性を考慮するとフュームドシリカがより好ましく、該フュームドシリカの中でも親水性フュームドシリカが更に好ましい。
なかでも、透明性表面保護層2は、必要に応じて、抗菌剤、抗ウイルス剤、及び、抗アレルゲン剤の少なくとも1種を含有することが好ましい。
有機系の抗菌剤や抗ウイルス剤としては、第4級アンモニウム塩系、第4級ホスホニウム塩系、ピリジン系、ピリチオン系、ベンゾイミダゾール系、有機ヨード系、イソチアゾリン系、アニオン系、エーテル系等がある。
無機系の抗菌剤や抗ウイルス剤としては、銀、銅、亜鉛等の金属イオンをゼオライト、アパタイト、ジルコニア、ガラス、酸化モリブデン等に担持させたものが挙げられる。
なお、上記抗菌剤や抗ウイルス剤は、1種単独で用いてもよいし、2種以上を混合して用いてもよい。
上記「粒子形状を保つ」とは、つまり透明性表面保護層2の硬化型樹脂となる組成物(硬化前の硬化性樹脂組成物)内で溶解することなく、粒子の状態で存在する。このため、透明性表面保護層2を形成する過程において、ベンゾイミダゾール系化合物の粒子又はアニオン系化合物の粒子が浮かび上がりやすくなり、透明性表面保護層2の最表面側にベンゾイミダゾール系化合物の粒子またはアニオン系化合物の粒子を偏在させやすくすることができる。
そして、透明性表面保護層2の最表面側にベンゾイミダゾール系化合物の粒子をまたはアニオン系化合物の粒子を偏在させることにより、所定の抗菌性、抗ウイルス性を得るために必要な抗菌剤や抗ウイルス剤の添加量を抑制することができるため、透明性表面保護層2の耐擦傷性の低下を抑制しやすくできる。
また、上記スチレンポリマー誘導体化合物及び不飽和カルボン酸誘導体化合物はスチレン、スルホン酸Na、アクリル酸、マレイン酸、フマル酸の構造の内少なくとも一種の構造を含むことが好ましく、全ての構造を含むことが更に好ましい。これは、ウイルスにはエンベロープ有無の2種類が存在し、それぞれに対し効果的に活性阻害しうる抗菌剤や抗ウイルス剤の構造は異なると考えられるためである。
そのため、例えば、ノンエンベロープウイルスであるインフルエンザウイルスのみの効果を期待するのであれば、スチレンポリマー誘導体化合物のみ含まれれば良く、その中でもスチレン樹脂単体のみ含まれれば十分に効果が得られる場合もある。
上記無機系の抗菌剤や抗ウイルス剤の平均粒子径としては、例えば0.1~10μmであることが好ましい。
上記平均粒子径であれば、上記抗菌剤や抗ウイルス剤が好適に分散して、抗菌性及び抗ウイルス性をムラが生じることなく好適に付与することができる。
例えば、上記酸化モリブデン銀複塩化合物に対しては、ベンゾトリアゾール化合物を用いると変色改善効果が期待できる。
なお、上記抗アレルゲン剤は、上記抗菌剤や抗ウイルス性を有するものであってもよい。
上記金属を担持してなる材料としては例えば、酸化チタン、リン酸カルシウム、珪酸カルシウム、リン酸ジルコニウム、ゼオライト、シリカアルミナ、珪酸マグネシウム及びリン酸マグネシウムからなる群から選択される少なくとも一種が好ましく、この中でも酸化チタン、リン酸ジルコニウム等が好ましい。
上記金属を担持してなる材料に担持される金属としては、例えば、金、銀、白金、亜鉛及び銅からなる群から選択される少なくとも一種が好ましく、この中でも銀、亜鉛等が好ましい。
市販品として例えば、大原パラヂウム社製「パラファインANV-100:無機化合物に銀担持」、日揮触媒社製「アトミーボールTZ-R:酸化チタンに亜鉛担持」、等を好適に用いることができ、この抗アレルゲン剤は、ダニや花粉など種々のアレルゲンに対して有効に作用するものである。
透明性表面保護層2の厚みが0.1μm未満であると、十分に耐久性(耐傷性、耐汚染性、耐候性等)を付与することができないことがあり、50μmを超えると、本発明の透明性樹脂フィルム10の透過率が低下し絵柄層の絵柄の視認性が低下してしまうことがある。
本発明の透明性樹脂フィルム10は、透明性樹脂層1の透明性表面保護層2側と反対側に接着用プライマー層3を有することが好ましい。
接着用プライマー層3を有することにより、基材の一方に積層された絵柄層との密着性を好適に付与することができる。
上記バインダー樹脂としては、例えば、ウレタン樹脂、アクリル樹脂、アクリル-ウレタン樹脂、アクリル-ウレタン共重合体樹脂、セルロース樹脂、ポリエステル樹脂、塩化ビニル-酢酸ビニル共重合体等が挙げられる。上述した表面保護層の電離放射線硬化型樹脂組成物にウレタンアクリレートオリゴマーを配合する場合は、表面保護層との接着性や生産時の効率からウレタン樹脂が好ましい。
上記接着用プライマー層3は、厚みが0.8μm以上、6μm以下であることがより好ましい。
なお、上記接着用プライマー層3は、必要に応じて、シリカ等の無機微粒子を含んでいてもよい。
上記透明性接着剤層としては、公知の接着剤を用いればよい。例えば、ポリウレタン、アクリル、ポリオレフィン、ポリ酢酸ビニル、ポリ塩化ビニル、塩化ビニル-酢酸ビニル共重合体、エチレン-アクリル酸共重合体、アイオノマー等のほか、ブタジエン-アクリルニトリルゴム、ネオプレンゴム、天然ゴム等が挙げられる。これら接着剤は、単独で又は2種以上を組み合わせて用いても良いし、2液硬化型、湿気硬化型、電離放射線硬化型、粘着剤(タック剤)といったものであってもよい。
上記透明性表面保護層用プライマー層を有することにより、透明性表面保護層2と透明性樹脂層1との密着性をより強固にすることができる。
上記透明性表面保護層用プライマー層は、上記紫外線吸収剤を含有してもよい。
上記透明性表面保護層用プライマー層としては、上述した接着用プライマー層と同様のものを好適に用いることができる。
透明性樹脂フィルム10は、後述する絵柄層が積層される側に凹凸形状を有してもよい。
透明性樹脂フィルム10が、後述する絵柄層が積層される側に凹凸形状を有する場合、その凹凸形状のJIS B 0601(2001)で定義されるRzmaxが、80μm以下であることが好ましい。
上記絵柄層が積層される側に有する凹凸形状のJIS B 0601(2001)で定義されるRzmaxが80μmを超えると、上記絵柄層と上記透明性樹脂フィルム10との間に気泡が入り込みやすくなり、本発明の化粧板の意匠性が低下することがある。
上記絵柄層が積層される側に有する凹凸形状のJIS B 0601(2001)で定義されるRzmaxが60μm以下であることがより好ましく、55μm以下であることが更に好ましく、50μm以下であることが特に好ましい。
なお、上記絵柄層が積層される側に有する凹凸形状のJIS B 0601(2001)で定義されるRzmaxの下限としては、例えば、15μmである。
なお、本明細書において、上記Rzmaxは、表面粗さ測定器(「SURFCOM-FLEX-50A」、東京精密社製)を用い、下記の条件で測定することにより得ることができる。
[測定条件]
測定回数:n=5(任意の5点)
算出規格:JIS′01
測定種別:粗さ測定
評価長さ:12.5mm
カットオフ値:2.5mm
測定速度:0.60mm/s
フィルタ種別:ガウシアン
形状除去:直線
λs値:8.0μm
凹凸形状に方向性がある場合には、流れ方向とその垂直方向を測定し、両者で数値の大きなものをRzmaxとする。
熱によるエンボス加工としては、例えば、周知の枚葉、又は、輪転式のエンボス機によるエンボス加工を施す方法が挙げられる。
また、エンボスの柄模様としては、例えば、砂目、ヘアライン、梨地、木目版導管溝、石板表面凹凸、布表面テクスチュア、万線条溝等が挙げられる。
また、エンボス加工する際の温度としては特に限定されないが、加熱圧着成形時に凹凸模様が消失する所謂エンボス戻りが少なくなる温度が好ましい。
また、上記絵柄層が積層される側に凹凸形状を有する場合、上記透明性樹脂フィルム10の双方の側について、上記方法により凹凸形状を形成しても良いし、上記透明性樹脂フィルム10の一方の側について、上記方法により凹凸形状を形成し、該一方の側に形成した凹凸形状に追従させて他方の側の凹凸形状を形成しても良い。
後述する絵柄層に積層される側と反対側に凹凸形状としては、例えば、JIS B 0601(1982)に規定される中心線平均粗さRaが1μm以上30μm以下の範囲内になるように適宜調整することが好ましい。
ここで、上記「凹凸形状の凹部」について説明する。
上記「凹凸形状の凹部」とは、透明性樹脂フィルム10の厚みのうち最も薄い部分を指すものであり、図3に示したように、透明性表面保護層2の凹凸形状の最も深い凹部を含む部分であり、透明性樹脂フィルム10の断面を顕微鏡観察することにより、確認することができる。なお、透明性樹脂層1の透明性表面保護層2側の凹凸形状の最も深い凹部の底から、反対側の面までの長さが「凹凸形状の凹部の厚み」である。
なお、透明性表面保護層2側の面から凹凸形状を形成することで、反対側の面にまで凹凸形状が生じている場合には、図4に示すように、透明性樹脂層1の透明性表面保護層2側の凹凸形状の最も深い凹部に対応して反対側の面には突起部が発生することになるが、透明性樹脂層1の透明性表面保護層2側の凹凸形状の最も深い凹部の底から、このような突起部の存在する反対側の面までの長さが「凹凸形状の凹部の厚み」となる。
上記透明性樹脂フィルム10の凹凸形状の凹部の厚みの上限は特に限定されないが、例えば、500μmであることが好ましい。
なお、図3に示したように、透明性表面保護層2を有する側の面から、反対側の面までの長さが透明性樹脂フィルム10の総厚みである。該総厚みの好ましい下限は100μm、好ましい上限は500μmであり、より好ましい下限は140μm、より好ましい上限は460μmである。
このようなベシクル化処理方法について簡単に説明すると、上記Bangham法は、フラスコなどの容器にクロロホルムまたはクロロホルム/メタノール混合溶媒を入れ、さらにリン脂質を入れて溶解する。その後、エバポレータを用いて溶媒を除去して脂質からなる薄膜を形成し、添加剤の分散液を加えた後、ボルテックスミキサーで水和・分散させることよりベシクルを得る方法である。
上記エクストルージョン法は、薄膜のリン脂質溶液を調液し、上記Bangham法において外部摂動として用いたミキサーに代わってフィルターを通過させることによりベシクルを得る方法である。
上記水和法は、上記Bangham法とほぼ同じ調製方法であるが、ミキサーを用いずに、穏やかに攪拌して分散させてベシクルを得る方法である。
上記逆相蒸発法は、リン脂質をジエチルエーテルやクロロホルムに溶解し、添加剤を含んだ溶液を加えてW/Oエマルジョンを作り、当該エマルジョンから減圧下において有機溶媒を除去した後、水を添加することによりベシクルを得る方法である。
上記凍結融解法は、外部摂動として冷却・加熱を用いる方法であり、この冷却・加熱を繰り返すことによってベシクルを得る方法である
上記超臨界逆相蒸発法とは、超臨界状態又は超臨界点以上の温度若しくは圧力条件下の二酸化炭素にベシクルの外膜を形成する物質を均一に溶解させた混合物中に、水溶性または親水性の封入物質としての各種添加剤を含む水相を加えて、一層の膜で封入物質としての各種添加剤を包含したカプセル状のベシクルを形成する方法である。
なお、超臨界状態の二酸化炭素とは、臨界温度(30.98℃)および臨界圧力(7.3773±0.0030MPa)以上の超臨界状態にある二酸化炭素を意味し、臨界点以上の温度若しくは圧力条件下の二酸化炭素とは、臨界温度のみ、又は、臨界圧力のみが臨界条件を超えた条件下の二酸化炭素を意味する。当該方法により、直径50~800nmの単層ラメラベシクルを得ることができる。
一般に、ベシクルとは、球殻状に閉じた膜構造を有する小胞の内部に液相を含むものの総称であり、特に、外膜がリン脂質等の生体脂質から構成されるものをリポソームと称する。
本発明の透明性樹脂フィルム10の製造方法は、トリアジン系紫外線吸収剤を含有する透明性樹脂層を準備する準備工程、透明性樹脂層の一方の面に、電離放射線硬化型樹脂を塗布する塗布工程、及び、電離放射線硬化型樹脂に電子線を照射する照射工程を有することを特徴とする。
透明性樹脂フィルム10の透明性表面保護層2を有する側の透明性樹脂層1aがトリアジン系紫外線吸収剤を含有することにより、照射工程における電子線の照射による黄変をより好適に抑制し、耐候性を好適に付与することができ、かつ、後述する絵柄層との密着性をより好適に付与することができる。
上記塗布工程において、トリアジン系紫外線吸収剤を含有する電離放射線硬化型樹脂を塗布することにより、透明性表面保護層2を形成することができる。
透明性樹脂フィルム10の透明性表面保護層2がトリアジン系紫外線吸収剤を含有することにより、上述した黄変を抑制でき、耐候性を好適に付与することができる。
なお、上記塗布工程における電離放射線硬化型樹脂の塗布量としては、上述した透明性表面保護層2の厚みの好ましい範囲となるように制御すればよい。
電離放射線の照射量としては、例えば、1~10Mrad程度であることが好ましい。
また、紫外線を用いることもでき、例えば、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライト、メタルハライドランプ等の光源を使用し、190~380nmの波長域で照射を行ってもよい。
上記熱ラミネート方式としては、Tダイを用いた溶融共押出し法等の公知の方法を用いることができる。
化粧板としては、絵柄層を有する基材上に、本発明の透明性樹脂フィルムが積層されている。
図5は、化粧板の一例を模式的示す断面図である。
化粧板20は、基材11の一方に積層された絵柄層12を有しており、絵柄層12と、本発明の透明性樹脂フィルム10とが、接着剤層13を介して積層された構造を有する。
以下、各構成について説明する。
基材11としては、特に限定されないが、例えば、化粧板の用途に合わせて適宜決定される。
基材11を構成する材料としては特に限定されず、例えば、樹脂材料、木質材料、金属材料等公知の材料が挙げられる。その中でも、上記基材を構成する材料としては、剛性や軽さを備える樹脂材料や木質材料が好ましい。また、これらの複合材料であっても良い。
上記樹脂材料としては、例えば、熱可塑性樹脂を含有することが好ましい。
上記熱可塑性樹脂としては、ポリ塩化ビニル樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂などのポリビニル樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、エチレン-酢酸ビニル共重合体樹脂(EVA)、エチレン-(メタ)アクリル酸系樹脂などのポリオレフィン樹脂、ポリエチレンテレフタレート樹脂(PET樹脂)などのポリエステル樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、アクリロニトリル-ブタジエンースチレン共重合体樹脂(ABS樹脂)、アクリロニトリル-スチレン共重合体樹脂などの熱可塑性樹脂の単体及び共重合体、スチレンブタジエンゴム、イソプレンゴム、クロロプレンゴムなどのジエン系ゴム、ブチルゴム、エチレンプロピレンゴムなどの非ジエン系ゴム、天然ゴム、熱可塑性エラストマーあるいは、これらの混合樹脂が好ましく挙げられる。なかでも、ポリオレフィン樹脂やアクリロニトリル-ブタジエン-スチレン共重合体樹脂、ポリ塩化ビニル樹脂、アイオノマー等が好ましい。更に、上記樹脂材料は、発泡されていてもよい。
上記金属材料としては、例えば、鉄、アルミニウム等が挙げられる。
また、基材11は、必要に応じて、着色剤(顔料又は染料)、木粉や炭酸カルシウム等の充填剤、シリカ等の艶消し剤、発泡剤、難燃剤、タルク等の滑剤、帯電防止剤、酸化防止剤、紫外線吸収剤、光安定剤等の各種の添加剤が含まれていてもよい。
基材11の厚みとしては特に限定されず、例えば、0.01mm以上が好ましく、0.1mm以上50mm以下がより好ましい。
なお、基材11は、平板以外の略板状も含み、凹凸や曲面を備えているものも含まれる。
なお、基材11が1mm以下と薄い場合には後述する被着材を基材11の裏面に設けてもよい。
絵柄層12は、化粧板に装飾性を付与する層であり、例えば、均一に着色が施された隠蔽層(ベタ印刷層)でもよいし、種々の模様をインキと印刷機を使用して印刷することにより形成される図柄層であってもよいし、隠蔽層と図柄層とを組み合わせた層(以下、模様層)であってもよい。
また、図柄層を設けることで、木目模様、大理石模様(例えばトラバーチン大理石模様)などの岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様など、あるいはこれらを複合した寄木、パッチワーク、文字、記号、抽象模様、草花模様、風景、キャラクターなどの模様を化粧板に付与することができる。これらの模様は通常の黄色、赤色、青色、及び黒色のプロセスカラーによる多色印刷によって形成される他、模様を構成する個々の色の版を用意して行う特色による多色印刷などによっても形成される。
また、上記着色剤としては、カーボンブラック(墨)、鉄黒、チタン白、アンチモン白、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルーなどの無機顔料、キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルーなどの有機顔料、又は染料、アルミニウム、真鍮などの鱗片状箔片からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛などの鱗片状箔片からなる真珠光沢(パール)顔料などが好ましく挙げられる。
上記接着剤層及び上記プライマー層は、透明性樹脂フィルム10で記載したものと同様のものを好適に用いることができる。
上記バッカー層としては、合成樹脂バッカー層及び発泡樹脂バッカー層等の樹脂バッカー層やコルクなど木質系バッカー層、不織布系バッカー層等が挙げられ、基材11の最下層(透明性樹脂フィルム10が積層される側と反対側)に有することが好ましい。
基材11が上記バッカー層を有することにより、化粧板の耐傷性、耐衝撃性をより一層向上することができる。
上記中空ビーズの種類、粒子径、及び、含有量等は、特開2014-188941号公報に記載のものを適用することができる。
上記難燃剤としては、透明性樹脂フィルム10で記載したものを適宜選択して用いることができる。
上記発泡樹脂バッカー層は、特開2014-188941号公報に記載のものを適用することができる。
基材11が薄い場合(例えば1mm以下)には、被着材を裏面(透明性樹脂フィルム10を有する側と反対側)に設けてもよい。
なお、上記被着材の厚みは特に限定されない。
本発明の化粧板の製造方法は、絵柄層が積層された基材と、本発明の透明性樹脂フィルムとをこの順に備える化粧板の製造方法であって、上記透明性樹脂フィルムの絵柄層が積層される側の面に接着剤層を形成する工程、及び、上記接着剤層を介して、上記透明性樹脂フィルムと上記絵柄層とを貼り合わせる工程を有することを特徴とする。
本発明の化粧板20の製造方法では、透明性樹脂フィルム10の絵柄層12に積層される側の面に接着剤層13を形成する工程を有するので、絵柄層12に積層される側の凹凸形状の凹部にも接着剤層13を入り込ますことができ、上述したエアガミの発生を防止し、意匠性の低下を抑制することができる。
化粧板20の厚みとしては特に限定されず、例えば、0.05mm以上が好ましく、1mm以上50mm以下であることがより好ましい。
透明性ポリプロピレンフィルム(厚さ60μm、透明性樹脂層bともいう)を準備し、透明性樹脂層bの片面に2液硬化型ウレタン樹脂の接着用プライマー剤を塗工し、接着用プライマー層(厚さ2μm)を形成した。
次いで、透明性樹脂層bの片面(接着用プライマー層と反対側)に、トリアジン系紫外線吸収剤を含有する透明性ポリプロピレン系樹脂(厚さ100μm、透明性樹脂層aともいう)を押し出し熱ラミネート方式で積層した。透明性樹脂層aの表面にコロナ処理を施した後、2液硬化型ウレタンアクリル共重合樹脂のプライマー剤(厚さ2μm)を塗工して、表面保護層用プライマー層を形成した。
その後、表面保護層用プライマー層の表面に、トリアジン系紫外線吸収剤を含有する電離放射線硬化型樹脂(塗布量15μm)をグラビアコート方式で塗工した後、電子照射装置を用いて加速電圧165keV、30KGyの条件で電子線を照射し透明性表面保護層を形成した。
その後、透明性表面保護層側を赤外線非接触方式のヒーターで加熱し、透明性樹脂層a及び透明性樹脂層bを柔らかくした後、直ちに熱圧によるエンボス加工を行い、凹凸形状を賦形して、透明性樹脂フィルムを作製した。
透明性樹脂層(a及びb)の厚みと、透明性表面保護層の紫外線吸収剤の含有量を表1に示した。
なお、透明性樹脂フィルムの絵柄層に積層される側と反対側に有する凹凸形状の凹部の厚みは、100μmであった。また、透明性樹脂フィルムの絵柄層が積層される側の凹凸形状は、JIS B 0601(2001)で定義されるRzmaxが、40μmであった。
上記「凹凸形状の凹部の厚み」及びRzmaxは、本明細書に記載の方法を用いて測定した。
押し出し熱ラミネート方式で積層する透明性樹脂層aにおいて、押し出し厚みを60μmにしたこと以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
得られた透明性樹脂フィルムの凹凸形状の凹部の厚み、透明性樹脂フィルムの絵柄層が積層される側のJIS B 0601(2001)で定義されるRzmaxは表3に示す通りであった。
紫外線吸収剤の含有量を表1のように変更した以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
透明性樹脂層(a及びb)の厚み、並びに、透明性表面保護層に含有される紫外線吸収剤をベンゾトリアゾール系紫外線吸収剤に変更し、その含有量を表1に記載のように変更した以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
紫外線吸収剤の含有量を表1に記載のように変更した以外は、比較例1と同様にして透明性樹脂フィルムを作製した。
透明性樹脂層(a及びb)の厚みの変更、並びに、透明性表面保護層において、紫外線吸収剤を含有しないこと以外は、比較例1と同様にして透明性樹脂フィルムを作製した。
押し出し熱ラミネート方式で積層する透明性樹脂層aにおいて、透明性ポリプロピレン系樹脂100部に対し、ホスフィン酸金属塩系難燃剤(Pekoflam STC アークロマ社製)10部添加したこと以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
なお、上記難燃剤の含有量は、透明性樹脂層(a及びb)の質量の合計を100質量%として、5.7質量%であった。
難燃剤をホスファゼン系難燃剤(ラビトルFP-100、伏見製薬所製)に変更した以外は、実施例4と同様にして透明性樹脂フィルムを作製した。
なお、上記難燃剤の含有量は、透明性樹脂層(a及びb)の質量の合計を100質量%として、5.7質量%であった。
透明性樹脂層aにおいて、透明性ポリプロピレン系樹脂100部に対し、ホスフィン酸金属塩系難燃剤(Pekoflam STC アークロマ社製)30部添加したこと以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
なお、上記難燃剤の含有量は、透明性樹脂層(a及びb)の質量の合計を100質量%として、14.4質量%であった。
実施例1とは異なる深いエンボス版にてエンボス加工を行ったこと以外は実施例1と同様に透明性樹脂フィルムを作製した。得られた透明性樹脂フィルムの凹凸形状の凹部の厚み、透明性樹脂フィルムの絵柄層が積層される側のJIS B 0601(2001)で定義されるRzmaxは表3に示す通りであった。
実施例7と同じ深いエンボス版を用いた以外は実施例2と同様に透明性樹脂フィルムを作製した。
得られた透明性樹脂フィルムの凹凸形状の凹部の厚み、透明性樹脂フィルムの絵柄層が積層される側のJIS B 0601(2001)で定義されるRzmaxは表3に示す通りであった。
電離放射線硬化型樹脂100重量部に対し、抗ウイルス剤としてリン酸系ガラス銀担持化合物(興亜硝子社製/PG-711)を3質量部添加したこと以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
電離放射線硬化型樹脂に対し、抗アレルゲン性を有するアニオン性フェノール系材料(DIC社製「EXP20530A」)を固形分比23質量%で配合し、抗アレルゲン性を有する亜鉛系材料(DIC社製「EXP20530B」)を固形分比23質量%で配合したこと以外は、実施例1と同様にして透明性樹脂フィルムを作製した。
実施例及び比較例において、電離放射線硬化型樹脂を塗工する前の状態のもの(透明性樹脂層(a及びb)と、接着用プライマー層とが形成された状態)を試験用フィルムとした。
試験用フィルムを標準白色板上に置き、下記の方法によりL1 *、a1 *、及びb1 *を測定した。
次いで、試験用フィルムに対して、電子照射装置を用いて加速電圧165keV、30KGyの条件で電子線を照射した。その後、電子線を照射した後の試験用フィルムを標準白色板上に置き、下記の方法によりL2 *、a2 *、及びb2 *を測定した。
なお、上記「L*、a*、b*」は、CIE(国際照明委員会)で規格化され、JIS Z8781-4:2013で採用されている表色系における「L*、a*、b*」を意味する。
[測定方法]
色彩色差計(コニカミノルタジャパン株式会社製 CR-400)を使用して、透明性樹脂フィルムの透明性樹脂層b側の表面へ入射角10度(表面の法線方向を0度とする)で光(D65光源)を照射し、全光線反射光(鏡面反射光+拡散反射光)に基づいて測定した。
上記測定した数値を下記式に代入することにより算出し、ΔEについては、下記の評価基準により評価した。その結果を表1に示した。
色差ΔE=((L1 *-L2 *)2+(a1 *-a2 *)2+(b1 *-b2 *)2)1/2
Δb=b1 *-b2 *
[評価基準]
(ΔEの評価基準)
++:ΔE<1.0
+:1.0≦ΔE≦2.0
-:2.0<ΔE
得られた透明性樹脂フィルムの接着用プライマー層側が、ダイレクトプリントした木質基材の装飾面(絵柄層)と接するようにしてラミネートし化粧板を作製した。
[水平燃焼性試験(難燃性:火の燃え広がり難さ)]
実施例1、4~6で得られた化粧板を9cm×30cmの大きさに切り出し、試験片とした。
図6(a)及び(b)のように、市販の家庭用ヒーター101(電圧AC100V、消費電力1200W)の台102の上に金属製の長方形の台103を置き、台の上に設置した金属製の枠104内に試験片105を置いて、ヒーター角45°、ヒーター出力を4/5の出力で火の燃え広がり難さの試験を行った。
詳細には、試験片を上記家庭用ヒーターを用いて2分間予熱した。次いで、図6(a)のように、試験片の長手方向のヒーター側の端部106にライター107で1分間加熱して着火して、図6(b)のように試験片105の長手方向に延焼させた。
次いで、延焼状態を目視で観察し、以下のように延焼距離(L1)、及び、燃焼継続時間を評価した。その結果を表2に示した。
[延焼距離(L1)]
試験片に着火してライターの火を除いた、初期着火からの延焼進行距離を測定して延焼距離(L1)とし、下記評価基準に従って評価した。なお、+評価以上であれば、実使用において問題ないと評価される。
+:L1が10cm未満である
-:L1が10cm以上である
[燃焼継続時間]
試験片に着火してライターの火を除いた、初期着火から自己消火する迄の燃焼継続時間を測定し、下記評価基準に従って評価した。なお、+評価以上であれば、実使用において問題ないと評価される。
+++:燃焼継続時間が100秒未満であるか、又は、着火しない
++:燃焼継続時間が100秒以上300秒未満である
+:燃焼継続時間が300秒以上600秒未満である
-:燃焼継続時間が600秒以上である(600秒で自己消化しない)
実施例1~2及び実施例7~8で得られた化粧板について、フローリングの日本農林規格;摩耗A試験に準拠し、テーバー式摩耗試験機(理学工業(株)製)と摩耗輪(S-42)を用いて荷重1kgで試験を行い、1000回転させた時の絵柄模様層の柄残りを評価した。その結果を表3に示した。
++:絵柄模様層が8割以上残っている
+:絵柄模様層が半分以上8割未満残っている
-:絵柄模様層が半分未満残っている
実施例1~2及び実施例7~8で得られた化粧板について、印刷柄を目視にて評価した。その結果を表3に示した。
++:印刷柄が明瞭に見える
+:印刷柄が僅かに曇って見える
-:印刷柄が明瞭に見えない
実施例1及び実施例9で作製した透明性樹脂フィルムについて、抗ウイルス試験方法(ISO21702)に準拠した方法で抗ウイルス性能試験を実施し、インフルエンザウイルスに対する抗ウイルス活性値を評価した。その結果を表4に示した。
+:抗ウイルス活性値2.0以上
-:抗ウイルス活性値2.0未満
実施例1及び実施例10で作製した透明性樹脂フィルムを細かく切断し、ダニアレルゲン水溶液中に1日間浸した後のアレルゲン量を水平展開クロマト法(マイティチェッカー)で目視にて確認した。その結果を表5に示した。
+:アレルゲン量の減少が確認できた
-:アレルゲン量の減少が確認できなかった
また、透明性樹脂層が難燃剤を含有する実施例4~6では、難燃性に優れることが確認された。
さらに、透明性樹脂フィルムが有する凹凸形状の凹部の厚みが80μm以上である実施例1、2及び8は耐摩耗性においても優れており、絵柄層が積層される側の凹凸形状のRzmaxが80μm以下である実施例1、2及び7は意匠性において優れており、Rzmaxが50μm以下である実施例1では意匠性において特に優れていた。
また、透明性表面保護層が抗菌剤や抗ウイルス剤を含む実施例9では、抗菌剤や抗ウイルス性を有することが確認され、透明性表面保護層が抗アレルゲン剤を含む実施例10では、抗アレルゲン性を有することが確認された。
一方で、透明性樹脂フィルムがベンゾトリアゾール系紫外線吸収剤を含有する比較例では、透明性表面保護層を形成する際に電子線を照射により黄変が生じていた。
また、本発明の透明性樹脂フィルムを用いた本発明の化粧板は、例えば、壁、天井、床等の建築物の内装材;窓枠、扉、手すり等の建具;家具;家電製品、OA機器等の筐体;玄関ドア等の外装材として好適に用いることができる。
1a 透明性樹脂層
1b 透明性樹脂層
2 透明性表面保護層
3 接着用プライマー層
10 透明性樹脂フィルム
11 基材
12 絵柄層
13 接着剤層
20 化粧板
101 家庭用ヒーター
102 家庭用ヒーターの台
103 長方形の台
104 金属製の枠
105 試験片
106 端部
107 ライター
Claims (16)
- 基材の一方に積層された絵柄層を保護するための透明性樹脂フィルムであって、
前記絵柄層に積層される側と反対側に凹凸形状を有しており、
少なくとも透明性樹脂層と、透明性表面保護層とがこの順に積層されており、
前記透明性表面保護層は、電離放射線硬化型樹脂からなり、
前記透明性樹脂層及び/又は前記透明性表面保護層は、トリアジン系紫外線吸収剤を含有する
ことを特徴とする透明性樹脂フィルム。 - 前記凹凸形状の凹部の厚みは、80μm以上である請求項1記載の透明性樹脂フィルム。
- 前記透明性樹脂フィルムは、前記絵柄層が積層される側に凹凸形状を有し、前記絵柄層が積層される側に凹凸形状のJIS B 0601(2001)で定義されるRzmaxが、80μm以下である請求項1又は2記載の透明性樹脂フィルム。
- 前記透明性樹脂層の前記透明性表面保護層側と反対側に接着用プライマー層を有する請求項1~3の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性樹脂層は、熱可塑性樹脂からなる請求項1~4の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性樹脂層は、少なくとも2層構成である請求項1~5の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性樹脂層は、難燃剤を含有する請求項1~6の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性表面保護層は、難燃剤を含有する請求項1~7の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性樹脂層のうち前記難燃剤を含有する層は、充填剤を含有する請求項7に記載の透明性樹脂フィルム。
- 前記難燃剤は、ホスフィン酸金属塩系難燃剤、ホスファゼン系難燃剤及びNOR型ヒンダードアミン系難燃剤からなる群より選択される少なくとも1種である請求項7~9の何れか1項に記載の透明性樹脂フィルム。
- 前記透明性表面保護層は、抗菌剤、抗ウイルス剤、及び、抗アレルゲン剤の少なくとも1種を含有する請求項1~10の何れか1項に記載の透明性樹脂フィルム。
- 請求項1~11の何れか1項に記載の透明性樹脂フィルムと絵柄層を備えた基材とが設けられた化粧板。
- トリアジン系紫外線吸収剤を含有する透明性樹脂層を準備する準備工程、
前記透明性樹脂層の一方の面に、電離放射線硬化型樹脂を塗布する塗布工程、及び、
前記電離放射線硬化型樹脂に電子線を照射する照射工程を有する
ことを特徴とする透明性樹脂フィルムの製造方法。 - 前記準備工程は、熱可塑性樹脂を準備し、前記熱可塑性樹脂の一方にトリアジン系紫外線吸収剤を含有する熱可塑性樹脂を積層して、透明性樹脂層を得る工程である請求項13に記載の透明性樹脂フィルムの製造方法。
- 前記電離放射線硬化型樹脂は、トリアジン系紫外線吸収剤を含有する請求項13又は14に記載の透明性樹脂フィルムの製造方法。
- 絵柄層が積層された基材と、請求項1~11のいずれかに記載の透明性樹脂フィルムとをこの順に備える化粧板の製造方法であって、
前記透明性樹脂フィルムの絵柄層が積層される側の面に接着剤層を形成する工程、及び、
前記接着剤層を介して、前記透明性樹脂フィルムと前記絵柄層とを貼り合わせる工程を有する
ことを特徴とする化粧板の製造方法。
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