WO2020075565A1 - 透明性樹脂フィルム、化粧板及び化粧板の製造方法 - Google Patents

透明性樹脂フィルム、化粧板及び化粧板の製造方法 Download PDF

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Publication number
WO2020075565A1
WO2020075565A1 PCT/JP2019/038611 JP2019038611W WO2020075565A1 WO 2020075565 A1 WO2020075565 A1 WO 2020075565A1 JP 2019038611 W JP2019038611 W JP 2019038611W WO 2020075565 A1 WO2020075565 A1 WO 2020075565A1
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Prior art keywords
layer
resin film
transparent resin
haze
resin
Prior art date
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PCT/JP2019/038611
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English (en)
French (fr)
Inventor
古田 哲
藤井 亮
智美 中島
義昭 根津
利成 茅原
陽亮 住田
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to KR1020217013265A priority Critical patent/KR20210069697A/ko
Priority to US17/283,733 priority patent/US20210379873A1/en
Priority to CN201980067162.8A priority patent/CN112839807B/zh
Priority to EP19871638.3A priority patent/EP3865298A4/en
Publication of WO2020075565A1 publication Critical patent/WO2020075565A1/ja

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Definitions

  • the present invention relates to a transparent resin film, a decorative board using the transparent resin film, and a method for producing the decorative board.
  • the inkjet printing method has an advantage that the substrate to be printed is not limited to the film, and printing can be performed on a substrate having a flat plate, unevenness, or a curved surface.
  • the pattern layer printed by the inkjet printing method is usually on the outermost surface of the substrate, surface performance such as scratch resistance, stain resistance, and weather resistance is insufficient, so that the pattern layer is protected.
  • Patent Document 1 an overcoat in which a protective layer is provided on one surface of transparent polypropylene containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer and an adhesive layer is provided on the other surface Laminate films are disclosed.
  • the present invention provides a transparent resin film capable of visually confirming a close contact state when laminated on a pattern layer provided on a base material, a decorative board using the transparent resin film, and a method for producing the decorative board.
  • the purpose is to provide.
  • the present inventors have provided a transparent resin film with a pattern layer of the base material by providing an external haze layer on the surface on the side laminated with the pattern layer of the base material.
  • a transparent resin film is laminated on the surface of, it is possible to easily visually judge whether or not air is caught, and if the air is caught, the adhesion with the above-mentioned pattern layer is lowered.
  • the inventors have found that by excluding it, it is possible to obtain a transparent resin film that can easily be made to have excellent adhesion to the above-mentioned pattern layer, and have completed the present invention.
  • the present invention is a transparent resin film for protecting a pattern layer laminated on one side of a substrate, wherein the transparent resin film is at least a thermoplastic resin layer and a side laminated on the pattern layer. It is a transparent resin film having an external haze layer.
  • the external haze layer preferably has a haze value of 4% or more and less than 100%.
  • a state in which a polyethylene terephthalate film having a haze value of 0.1% or less is attached to the side opposite to the thermoplastic resin layer side of the external haze layer through a pure water layer, and the back surface measured from the thermoplastic resin layer side is wet. It is preferable that the haze value is 90% or less.
  • the thickness of the outer haze layer is preferably 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the transparent resin film has a concavo-convex shape on the side opposite to the side laminated on the pattern layer, and the haze value is the haze value excluding the surface haze on the side opposite to the side laminated on the pattern layer.
  • (1) is 70% or more and is a haze value (2) which is a haze value excluding the surface haze on the side laminated on the pattern layer and the surface haze on the side opposite to the side laminated on the pattern layer.
  • the present invention is also a decorative board including a base material, a pattern layer, and the transparent resin film of the present invention in order in the thickness direction.
  • the present invention is a method for producing a decorative board of the present invention, wherein a step of forming an adhesive layer on the surface of the transparent resin film on which the pattern layer is laminated, and the above-mentioned adhesive layer, It is also a method of manufacturing a decorative board, which has a step of bonding a transparent resin film and the pattern layer.
  • the transparent resin film of the present invention Since the transparent resin film of the present invention has an external haze layer on the surface of the base material on which the pattern layer is laminated, air is trapped when the transparent resin film is laminated on the surface of the base material pattern layer. It is possible to easily determine whether or not it is visible, and by excluding those whose adhesive force with the above-mentioned pattern layer is lowered due to air biting, those with excellent adhesiveness with the above-mentioned pattern layer It becomes easy to.
  • the decorative board of the present invention in which such a transparent resin film of the present invention is laminated on the surface of the pattern layer of the substrate can be easily formed in a state where air is not trapped between the pattern layer and the transparent resin film. It is possible to easily improve the adhesion between them.
  • the transparent resin film of the present invention will be described.
  • the lower and upper limits of the numerical range represented by “to” mean “greater than or equal to” (for example, ⁇ to ⁇ means ⁇ or more and ⁇ or less).
  • a preferred example of the transparent resin film of the present invention will be described with reference to the drawings.
  • the transparent resin film 10 of the present invention has at least a thermoplastic resin layer 11 and an external haze layer 12.
  • thermoplastic resin layer The thermoplastic resin forming the thermoplastic resin layer includes one or more of the following resins, and examples thereof include polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene) and ethylene- ⁇ -olefin copolymer.
  • the thermoplastic resin layer may be unstretched, but may be uniaxially stretched or biaxially stretched as necessary.
  • the thickness of the thermoplastic resin layer is not particularly limited, but the preferred lower limit is 20 ⁇ m, the preferred upper limit is 500 ⁇ m, the more preferred lower limit is 60 ⁇ m, and the more preferred upper limit is 420 ⁇ m. If the thickness of the thermoplastic resin layer is less than 20 ⁇ m, the tensile strength may be insufficient and the surface of the pattern layer may not be protected, and if it exceeds 500 ⁇ m, the transmittance of the transparent resin film of the present invention may decrease. The visibility of the picture in the picture layer may be reduced.
  • thermoplastic resin layer is not particularly limited as long as the pattern layer provided on the substrate can be seen, and may be colored.
  • a colorant may be added to the above halogen-free thermoplastic resin.
  • a pigment or a dye used in a pattern layer described later can be used.
  • the thermoplastic resin layer includes a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (for example, rubber. ) And other various additives may be included.
  • the thermoplastic resin layer When the thermoplastic resin layer has two or more layers, it may be laminated via a transparent adhesive layer or may be laminated by a thermal laminating method. Since the adhesive is not required and problems such as peeling due to deterioration of the adhesive do not occur, it is preferable that the layers are laminated by a thermal laminating method.
  • a known method such as a melt coextrusion method using a T die can be used.
  • a known adhesive may be used as the transparent adhesive layer.
  • These adhesives are used alone or in combination of two or more.
  • the thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 ⁇ m, more preferably about 1 to 5 ⁇ m.
  • quenching means that the transparent resin film is cooled at 200 ° C./sec or more.
  • the rapid cooling method include a method in which a metal roll cooled to 10 ° C. or less immediately after being laminated by a thermal laminating method is brought into contact with the metal roll for several seconds.
  • the quenching rate is preferably 230 ° C./second, more preferably 250 ° C./second.
  • the surface of the thermoplastic resin layer opposite to the surface on which the external haze layer is provided (hereinafter, also referred to as the back surface) (hereinafter, also referred to as the front surface) may be a smooth surface and has an uneven shape. May be. Since the surface is a smooth surface, the pattern layer laminated on one surface of the base material can be more clearly projected.
  • the smooth surface means a surface having a center line average roughness Ra of 2.0 ⁇ m or less defined in JIS B 0601 (1982).
  • the "surface” means the outermost surface of the transparent resin film (the side opposite to the side laminated on the picture layer), and when the transparent resin film has a surface protective layer described later, the surface protective layer is It means the outermost surface on the holding side.
  • the transparent resin film of the present invention can have a design feeling because the surface has an uneven shape, and makes the decorative board using the transparent resin film of the present invention more excellent in design. be able to.
  • the depth of the uneven shape to be formed is not particularly limited, but may be appropriately adjusted, for example, so that the center line average roughness Ra defined in JIS B 0601 (1982) is within the range of 5 to 20 ⁇ m. preferable.
  • the uneven shape preferably has a maximum height Rz defined by JIS B 0601 (2001) of 20 ⁇ m or more and 200 ⁇ m or less. Since the transparent resin film of the present invention has the above-mentioned concavo-convex shape, the designability can be improved more suitably. On the other hand, if the maximum height Rz is less than 20 ⁇ m, sufficient designability may not be imparted, and if it exceeds 200 ⁇ m, the shapeability of the uneven shape may deteriorate.
  • the maximum height Rz is preferably 50 ⁇ m or more and 180 ⁇ m or less, and more preferably 70 ⁇ m or more and 150 ⁇ m or less.
  • the center line average roughness Ra defined in JIS B 0601 (1982) and the maximum height Rz defined in JIS B 0601 (2001) are the surface roughness measuring device (“SURFCOM”).
  • SURFCOM surface roughness measuring device
  • -FLEX-50A manufactured by Tokyo Seimitsu Co., Ltd.
  • the method for forming the uneven shape on the surface of the thermoplastic resin layer is not particularly limited, and examples thereof include embossing by heat and a method of transferring the uneven shape to the thermoplastic resin layer by a shaping sheet.
  • embossing by heat for example, a well-known sheet-fed method or a method of performing embossing by a rotary embossing machine can be mentioned.
  • examples of the embossed pattern include grain, hairline, satin, woodgrain conduit groove, stone plate surface irregularities, cloth surface texture, and line groove. Also.
  • the temperature at the time of embossing is not particularly limited, but a temperature at which so-called emboss return that the uneven pattern disappears during thermocompression molding is reduced is preferable, for example, a sheet temperature of 120 ° C to 160 ° C, 1.0 to 4.0 MPa. Then, the uneven pattern may be transferred.
  • the transparent resin film When the transparent resin film is embossed, it may be formed after forming a surface protective layer described later or before forming the surface protective layer.
  • the surface protective layer may be formed, and finally embossing may be performed.
  • the thermoplastic resin layer After forming the thermoplastic resin layer, embossing may be performed, and finally the surface protective layer may be formed.
  • the thermoplastic resin layer may be formed, and at the same time, embossing may be performed, and finally, the surface protective layer may be formed.
  • the transparent resin film 10 of the present invention has a surface protective layer 14 on the surface of the thermoplastic resin layer 11 opposite to the external haze layer 12 via a surface protective layer primer layer 13. May be provided.
  • the transparent resin film of the present invention has more excellent durability (scratch resistance, stain resistance, weather resistance, etc.), and it becomes possible to more suitably protect the surface of the pattern layer. It is possible to suitably prevent the deterioration of the design property due to the scratch of the transparent resin film of the invention.
  • the surface protective layer may have a single layer structure or a plurality of layer structures made of the same or different materials.
  • the surface protective layer is not particularly limited, but includes, for example, a two-component curable resin or a crosslinked cured product of an ionizing radiation curable resin composition, and the crosslinked cured product is preferably transparent. As long as it is transparent, it may be translucent or colored as long as the pattern layer described later can be visually recognized.
  • Examples of the two-component curable resin include two-component curable urethane resin, two-component curable polyester resin, and two-component curable epoxy resin.
  • Examples of the ionizing radiation curable resin composition include an oligomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule (hereinafter, also referred to as so-called prepolymer, macromonomer, etc.) and / or in the molecule.
  • a monomer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group is preferably used as the monomer.
  • the ionizing radiation here means an electromagnetic wave or charged particles having energy capable of polymerizing or crosslinking 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 and a (meth) acryloyloxy group, and a cationically polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers may be used alone or in combination of two or more.
  • the (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 oligomer is more preferable.
  • the molecular weight is usually about 250 to 100,000.
  • a polyfunctional monomer for example, 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, trimethylolpropane.
  • the polyfunctional monomer refers to a monomer having a plurality of radically polymerizable unsaturated groups.
  • the above-mentioned ionizing radiation curable resin composition contains an ionizing radiation curable resin component composed of a urethane acrylate oligomer and a polyfunctional monomer, and as the ionizing radiation curable resin component, a urethane acrylate oligomer / polyfunctional It is particularly preferable that the monomer (mass ratio) is 6/4 to 9/1. Within this mass ratio range, scratch resistance can be made more excellent.
  • a monofunctional monomer may be appropriately used within a range not deviating from the object of the present invention. Examples of the monofunctional monomer include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
  • the above ionizing radiation-curable resin composition is cross-linked with ultraviolet rays, it is preferable to add a photopolymerization initiator to the ionizing radiation-curable resin composition.
  • a photopolymerization initiator acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers alone or in combination. Can be used.
  • the ionizing radiation curable resin composition is a resin system having a cationically polymerizable unsaturated group
  • the photopolymerization initiator an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metacerone compound, benzoin Sulfonic acid esters and the like can be used alone or as a mixture.
  • the amount of these photopolymerization initiators added is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation-curable resin component.
  • additives may be further added to the above ionizing radiation curable resin composition, if necessary.
  • 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, acrylic resin.
  • Thermoplastic resins such as cellulosic resins, lubricants such as silicone resins, waxes and fluororesins, UV absorbers such as benzotriazole and benzophenone, light stabilizers such as hindered amine radical scavengers, colorants such as dyes and pigments, etc. Is.
  • the electron beam source of ionizing radiation for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, or linear type, dynamitron type, high frequency type, etc. It is possible to use one that irradiates an electron having an energy of 70 to 1000 keV. Further, the irradiation dose of the electron beam is preferably, for example, about 1 to 10 Mrad.
  • the ultraviolet ray source of the ionizing radiation for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used, and the wavelength of the ultraviolet ray is usually 190 to 380 nm. The wavelength range is mainly used.
  • the surface protective layer primer layer preferably contains a binder resin.
  • the primer layer for the surface protective layer is preferably transparent, and may be translucent or colored as long as the pattern layer is visible as long as it is transparent.
  • the binder resin include urethane resins, acrylic resins, acryl-urethane resins (acryl-modified urethane resins), acryl-urethane copolymer resins (block copolymers, etc.), cellulose resins, urethane-cellulose resins (eg, , A resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton), a polyester resin, a vinyl chloride-vinyl acetate copolymer resin, and the like.
  • the urethane resin is preferable from the viewpoint of adhesion with the surface protective layer and efficiency
  • the primer layer for the surface protective layer preferably has a thickness of 0.5 ⁇ m or more and 10 ⁇ m or less. If it is 0.5 ⁇ m or more, the adhesiveness between the transparent resin film of the present invention and a pattern layer described later can be suitably secured, and if it is 10 ⁇ m or less, the transparent resin film of the present invention does not become too thick, which is sufficient. Transparency can be obtained, and the design of the decorative plate can be suitably secured. Also, blocking during film formation can be suppressed. Blocking is a phenomenon in which the transparent resin film is coated with a film-forming or adhesion primer or the like, rolled up into a roll, and the films become difficult to separate when unwound.
  • the primer layer for the surface protective layer may contain inorganic fine particles such as silica.
  • the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers and light stabilizers. The amount of the additive compounded can be appropriately set according to the product characteristics.
  • the transparent resin film of the present invention has an external haze layer.
  • the external haze layer is laminated on the back surface of the thermoplastic resin layer in order to protect the surface of the pattern layer laminated on one surface of the base material described later.
  • the haze value of the external haze layer is preferably 4% or more and less than 100%. When the haze value is less than 4%, air entrapment may not be visually recognizable when the transparent resin film of the present invention is laminated on the surface of the pattern layer, and the adhesion may be insufficient. is there.
  • a more preferable lower limit of the haze value of the outer haze layer is 5%, and a further preferable lower limit thereof is 6%.
  • the haze value of the external haze layer is a value obtained by subtracting the haze when the back surface is wet from the haze of the entire transparent resin film.
  • the haze of the entire transparent resin film can be measured using a known haze meter, for example, by shining light from the surface side of the external haze layer or from the surface side of the transparent resin film.
  • the haze in the wet state of the back surface is from the front surface side of the transparent resin film in the state where PET having a haze value of 0.1% or less is attached to the back surface side of the transparent resin film through pure water. It can be measured by shining light and using a known haze meter. By doing so, it is possible to calculate the haze value by removing the haze value of the external haze layer from the transparent resin film.
  • a polyethylene terephthalate film having a haze of 0.1% or less is attached to the side opposite to the thermoplastic resin layer side of the external haze layer via a pure water layer, and the thermoplastic resin layer side It is preferable that the haze value in the wet state of the back surface is 90% or less.
  • the haze value in the wet state of the back surface measured from the thermoplastic resin layer side exceeds 90%, the transparency of the transparent resin film of the present invention decreases and the visibility of the pattern layer when used as a decorative plate May be inferior to.
  • the more preferable upper limit of the haze value when the back surface is wet is 80%, and the more preferable upper limit thereof is 60%.
  • the material forming the external haze layer is a material used for better adhesion with the pattern layer, and examples thereof include urethane resin, acrylic resin, urethane-acrylic resin, urethane-acrylic copolymer resin, Cellulose resin, polyester resin, vinyl chloride-vinyl acetate copolymer and the like can be mentioned.
  • the outer haze layer preferably has a thickness of 0.5 ⁇ m or more and 20 ⁇ m or less. When it is less than 0.5 ⁇ m, the adhesion between the substrate and the transparent resin film is insufficient, while when it is more than 20 ⁇ m, when the transparent resin film is formed into a roll, the front and back of the film come into contact with each other. Blocking may occur.
  • the more preferable lower limit of the thickness of the outer haze layer is 0.8 ⁇ m, the more preferable upper limit thereof is 15 ⁇ m, the still more preferable lower limit thereof is 1 ⁇ m, and the still more preferable upper limit thereof is 10 ⁇ m.
  • Examples of the method for setting the haze value in the wet state of the back surface in the above range include, for example, a method of adjusting the amount of the additive contained in the thermoplastic resin layer and a method of reducing the thickness of the thermoplastic resin layer. Conceivable.
  • the external haze layer may be subjected to surface treatment such as corona discharge treatment or plasma treatment on the surface of the thermoplastic resin layer on which the external haze layer is provided, in order to further strengthen the adhesion with the thermoplastic resin layer. .
  • the surface treatment method and conditions may be carried out according to known methods.
  • a primer layer may be formed between the outer haze layer and the base material layer to enhance the adhesion.
  • the external haze layer may have a function as a primer layer for improving the adhesion with the base material layer and the thermoplastic resin layer.
  • the same one as the above-mentioned primer layer for surface protection layer can be preferably used.
  • the external haze layer may have a single layer or a plurality of layers similar to the thermoplastic resin layer on the surface opposite to the thermoplastic resin layer side. Moreover, you may mix
  • the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers and light stabilizers. The amount of the additive compounded can be appropriately set according to the product characteristics.
  • the transparent resin film of the present invention preferably has a haze value (hereinafter also referred to as haze value (1)) of 70% or more excluding the surface haze on the side opposite to the side laminated on the substrate. Since the transparent resin film of the present invention has such a haze, the heat absorptivity can be increased, and thus the shapeability of the uneven shape is excellent. Normally, the uneven shape formed by embossing or the like disappears due to heat or the passage of time. However, since the haze value (1) is within the predetermined range, the disappearance of such uneven shape is suppressed. can do.
  • the haze value (1) is more preferably 75% or more, further preferably 80% or more. In the present specification, the haze is a value measured by using DIRECT READING HAZE METER (manufactured by Toyo Seiki Co., Ltd.).
  • the haze value (1) can be measured by the following method. That is, a transparent resin film, pure water, and a PET film (haze value of 3% or less) are laminated in this order to produce a sheet. At this time, the pure water is laminated on the side of the transparent resin film having the uneven shape. Regarding the obtained sheet, from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, the DIRECT READING HAZE METER (Toyo Seiki Co., Ltd. Haze value of the PET film is excluded by measuring the haze value of the PET film, specifically, the haze value of the PET film (for example, 3%) can be subtracted.
  • the transparent resin film of the present invention excludes the surface haze on the side laminated on the substrate and the surface haze on the side opposite to the side laminated on the substrate (hereinafter, also referred to as haze value (2). ) Is preferably 70% or less. Since the transparent resin film of the present invention has such haze, the pattern formed on the pattern layer described later can be clearly seen, and thus the design is excellent.
  • the haze value (2) is more preferably 65% or less, further preferably 60% or less.
  • the haze value (2) can be measured by the following method. That is, a PET film (having a haze value of 3% or less), pure water, a transparent resin film, pure water, and a PET film (having a haze value of 3% or less) are laminated in this order to produce a sheet. Regarding the obtained sheet, from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, the DIRECT READING HAZE METER (Toyo Seiki Co., Ltd. Manufactured) to exclude the haze value of the PET film, specifically, to draw each PET film (for example, the haze value of the PET film is 3% each, and the total is 6%). Can be obtained by the following method. That is, a PET film (having a haze value of 3% or less), pure water, a transparent resin film, pure water, and a PET film (having a haze value of
  • the method for producing the transparent resin film of the present invention is not particularly limited, and a method of laminating each layer described above via the transparent adhesive layer or a primer layer for a surface protective layer, or laminating by a thermal laminating method Methods and the like.
  • a known method such as a melt coextrusion method using a T die can be used.
  • the transparent resin film of the present invention is used for protecting the above-mentioned pattern layer, and has an external haze layer on the surface of the substrate on the side laminated with the pattern layer, so that the surface of the pattern layer of the substrate is transparent.
  • the resin films are laminated, it is possible to easily visually judge whether or not air is trapped, and it is easy to improve the adhesiveness with the pattern layer.
  • a decorative board including a base material, a pattern layer, and the transparent resin film of the present invention in this order in the thickness direction is also an aspect of the present invention.
  • the pattern layer 24 is laminated on one surface of the base material 25, and the transparent resin film 10 of the present invention is laminated on the side of the pattern layer 24 opposite to the side having the base material 25.
  • the adhesive layer 23 it is preferable to have the adhesive layer 23.
  • the material forming the base material is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, and metal materials. Also, a composite material of these may be used.
  • the resin material preferably contains, for example, a thermoplastic resin.
  • the thermoplastic resin include polyvinyl chloride resins, polyvinyl acetate resins, polyvinyl resins such as polyvinyl alcohol resins, polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resins (EVA), ethylene- (meth) acrylic acid.
  • polyolefin resin such as base resin, polyester resin such as polyethylene terephthalate resin (PET resin), acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer
  • PET resin polyethylene terephthalate resin
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resin acrylonitrile-styrene copolymer
  • polyolefin resin, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride resin, ionomer and the like are preferable.
  • the resin material may be foamed.
  • examples of the wood material include various materials such as cedar, cypress, zelkova, pine, lauan, teak, and melapy
  • examples of the core material include a veneer made of these materials and a single piece of wood. Any of a board, a wood plywood (including LVL), a particle board, a medium density fiberboard (MDF), a high density fiberboard (HDF), a laminated material, or the like, or a laminated material in which these are appropriately laminated may be used.
  • Examples of the metal material include iron.
  • the base material may include an inorganic compound.
  • the types of resins forming the plurality of thermoplastic resin layers may be the same or different, and the thickness of the plurality of thermoplastic resin layers May be the same or different.
  • the base material may have a hollow structure, a slit groove or a through hole may be provided in a part of the base material, or a frame-shaped material obtained by combining the above materials.
  • the thickness of the substrate is not particularly limited, and is preferably 0.01 mm or more, more preferably 0.1 mm or more and 50 mm or less.
  • the base material has a substantially plate shape other than a flat plate, and includes a base material having irregularities and a curved surface.
  • the pattern layer provided on the base material is a layer that imparts decorative properties to the decorative board of the present invention that uses the transparent resin film of the present invention, and is, for example, a uniformly colored hiding layer (solid).
  • Print layer or a pattern layer formed by printing various patterns using an ink and a printing machine, or a layer in which a concealing layer and a pattern layer are combined (hereinafter, referred to as a pattern layer). ) May be sufficient.
  • the above-mentioned concealing layer when the above-mentioned base material is colored or has color unevenness, it is possible to give an intended color and adjust the surface color.
  • stone patterns that imitate the surface of rocks such as wood patterns, marble patterns (eg, travertine marble patterns), cloth patterns that imitate texture or cloth-like patterns, tile pasting patterns, brickwork A pattern or the like, or a pattern such as a parquet or a patchwork in which these are combined can be applied to the decorative sheet.
  • These patterns are formed by multicolor printing with normal process colors of yellow, red, blue, and black, and also by multicolor printing with special colors performed by preparing individual color plates that make up the pattern. To be done.
  • a binder resin in which a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst and a curing agent are appropriately mixed is used.
  • the binder resin is not particularly limited, and preferred examples thereof include urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin and nitrocellulose resin.
  • any of these may be used alone or in combination of two or more.
  • colorant carbon black (black ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red halo, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone Organic pigments such as yellow and phthalocyanine blue, metal pigments consisting of scale-like foil pieces such as dyes, aluminum and brass, pearlescent pigments consisting of scale-like foil pieces such as titanium dioxide coated mica and basic lead carbonate. are preferred.
  • the thickness of the pattern layer is not particularly limited, and is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more and 600 ⁇ m or less. When the thickness of the pattern layer is within the above range, an excellent design can be imparted to the decorative board of the present invention and concealing property can be imparted. When it is desired to make use of the design of the base material itself, such as a veneer, in which the base material itself has a design property, the base material itself also serves as the design layer, so that a separate design layer need not be provided. .
  • the transparent resin film of the present invention is used for protecting the surface of the pattern layer by laminating the external haze layer on the surface of the pattern layer laminated on one surface of the above-mentioned substrate.
  • a decorative board comprising a base material, a pattern layer, and the transparent resin film of the present invention in this order in the thickness direction is also one aspect of the present invention.
  • the thickness of the decorative board of the present invention is not particularly limited, and is preferably 0.05 mm or more, more preferably 1 mm or more and 50 mm or less.
  • the decorative board of the present invention may further have a backer layer or the like, if necessary.
  • the adherend may be provided on the back side of the transparent adhesive layer, the primer layer, the backer layer or the like.
  • the transparent adhesive layer and the primer layer the same ones as those described in the above-mentioned transparent resin film can be preferably used.
  • backer layer examples include a synthetic resin backer layer and a foamed resin backer layer, and it is preferable that the backer layer is provided on the lowermost layer of the base material (the side opposite to the side on which the transparent resin film is laminated).
  • the base material has the backer layer, the scratch resistance and impact resistance of the decorative board can be further improved.
  • Examples of the resin forming the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, and high heat-resistant polyalkylene terephthalate [eg, a part of ethylene glycol is 1 Polyethylene terephthalate substituted with 4-cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer , Amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS and the like. These resins can be used alone or in combination of two or more.
  • the synthetic resin backer layer may contain hollow beads.
  • the type, particle size, content and the like of the hollow beads those described in JP-A-2014-188941 can be applied.
  • 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 calender molding and extrusion molding of molten resin. Of these, extrusion molding of a molten resin is preferable, and for example, extrusion molding using a T die is more preferable.
  • the foamed resin backer layer may be provided below the synthetic resin backer layer (on the side opposite to the side having the uneven shape). As the foamed resin backer layer, those described in JP-A-2014-188941 can be applied.
  • the base material may be a support.
  • the support is not particularly limited, and various types of papers, plastic films, wood-based boards such as wood, ceramic materials, etc. can be appropriately selected according to the application. These materials may be used alone, or may be a laminate of any combination such as a composite of paper and a composite of paper and plastic film.
  • Examples of the papers include thin paper, kraft paper, titanium paper and the like. These paper base materials are used to strengthen the interlaminar strength between the paper base material or other layers of the paper base material and the paper base material, or to prevent fluffing, these paper base materials are further provided with an acrylic resin, a styrene butadiene rubber, Resins such as melamine resin and urethane resin may be added (impregnated with resin after papermaking or internally filled during papermaking). For example, inter-paper reinforcing paper, resin-impregnated paper and the like.
  • various papers often used in the field of building materials such as linter paper, paperboard, gypsum board base paper, vinyl wallpaper stock having a vinyl chloride resin layer provided on the surface of the paper, and the like can be mentioned.
  • coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, or Japanese paper used in the business field, ordinary printing, packaging, etc. can also be used.
  • woven or non-woven fabrics of various fibers having an appearance and properties similar to paper can also be used as the substrate.
  • various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, or vinylon fibers.
  • inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or carbon fibers
  • synthetic resin fibers such as polyester fibers, acrylic fibers, or vinylon fibers.
  • thermosetting resin When the above papers are impregnated with a thermosetting resin, conventionally known thermosetting resins can be widely used.
  • the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curing type polyurethane), epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine- Examples thereof include urea co-condensation resin, silicon resin, polysiloxane resin and the like.
  • the layer obtained by impregnating the above papers with the thermosetting resin is also referred to as a thermosetting resin layer.
  • the thermosetting resin may eventually serve as a surface protective layer.
  • thermosetting resin layer examples include a method of impregnating a porous substrate with the thermosetting resin when the support has a porous substrate.
  • the impregnation can be performed by supplying the above thermosetting resin from either or both of the front side and the back side of the porous substrate.
  • This method is not particularly limited, and for example, a method of immersing it in a bath containing a thermosetting resin from the surface of the porous substrate on which the release layer is formed or the surface opposite thereto; a coater such as a kiss coater or a comma coater
  • a coater such as a kiss coater or a comma coater
  • thermosetting resin is applied to the porous substrate by a spray device, a shower device, or the like.
  • the surface of the material on which the release layer is formed, the surface opposite to the surface, or a method of spraying on both surfaces thereof may be mentioned.
  • the resin that constitutes the plastic film include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins, vinylidene chloride resins, phenol resins, polyvinyl alcohol, vinyl resins such as ethylene-vinyl alcohol copolymer, and polyethylene.
  • Polyester resin such as terephthalate and polybutylene terephthalate, acrylic resin such as polymethyl methacrylate, polymethyl acrylate and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, polycarbonate, etc. Is mentioned.
  • a polyolefin resin, a vinyl chloride resin, a polyester resin, or an acrylic resin is preferable from the viewpoints of various physical properties such as weather resistance and water resistance, printability, moldability, and price.
  • the thickness of the support is not particularly limited, but when the support is a plastic film, it is preferably 20 to 200 ⁇ m, more preferably 40 to 160 ⁇ m, still more preferably 40 to 100 ⁇ m. If the support is paper, the basis weight, usually preferably 20 ⁇ 150g / m 2, more preferably 30 ⁇ 100g / m 2.
  • the shape of the support is not limited to a flat plate, and may be a special shape such as a three-dimensional shape.
  • one or both surfaces may be subjected to easy adhesion treatment such as physical treatment or chemical surface treatment.
  • the decorative board may be laminated with phenol resin-impregnated paper, if necessary.
  • the phenol resin-impregnated paper may be laminated on the surface of the porous substrate opposite to the side on which the abrasion resistant layer and the release layer are formed.
  • the above-mentioned phenol resin-impregnated paper is generally a core paper in which kraft paper having a basis weight of about 150 to 250 g / m 2 is impregnated with phenol resin at an impregnation rate of about 45 to 60% and dried at about 100 to 140 ° C. It is a paper manufactured by A commercial item can be used for the phenol resin impregnated paper.
  • the back surface of the porous substrate may be subjected to corona discharge treatment, or the back surface primer layer may be formed by applying the above-mentioned primer layer. .
  • sealer layer When a base material having an impregnating property such as paper is used as the support, a sealer layer may be provided between the support and the pattern layer.
  • the sealer layer preferably contains a cured product of a curable resin composition such as a thermosetting resin composition or an ionizing radiation curable resin composition, among which a cured product of the thermosetting resin composition is included. Is more preferable.
  • the content of the cured product of the curable resin composition is preferably 50% by mass or more, and more preferably 65 to 95% by mass based on the total solid content of the sealer layer.
  • the thermosetting resin composition and the ionizing radiation curable resin composition for the sealer layer include the same as those exemplified for the surface protective layer.
  • the thermosetting resin composition is preferably a two-component curable resin of polyol and isocyanate, more preferably a two-component curable resin of acrylic polyol and hexamethylene diisocyanate.
  • the sealer layer preferably contains particles from the viewpoint of drying suitability and viscosity adjustment.
  • the content of the particles is preferably 5 to 50% by mass of the total solid content of the sealer layer, and more preferably 5 to 35% by mass.
  • the particles of the sealer layer are preferably inorganic particles, of which silica is preferable.
  • the particles preferably have an average particle size of 0.1 to 2.0 ⁇ m, more preferably 0.2 to 1.5 ⁇ m.
  • the decorative board of the present invention may be used by being laminated on the adherend such that the side having the uneven shape and the opposite side are in contact with each other.
  • the decorative board of the present invention can be obtained by laminating the transparent resin film on the adherend having the pattern layer.
  • the above-mentioned pattern layer can be preferably used as the above-mentioned pattern layer.
  • the material of the adherend is, for example, wood veneer, wood plywood, particle board, wood board such as MDF (medium density fiber board); gypsum board such as gypsum board, gypsum slag board; calcium silicate board, asbestos slate board.
  • MDF medium density fiber board
  • gypsum board such as gypsum board, gypsum slag board
  • calcium silicate board asbestos slate board.
  • Cement boards such as lightweight foamed concrete boards and hollow extruded cement boards; fiber cement boards such as pulp cement boards, asbestos cement boards and wood chip cement boards; ceramics boards such as pottery, porcelain, earthenware, glass, enamel; iron plates, zinc plating Steel plates, metal plates such as polyvinyl chloride sol-coated steel plates, aluminum plates, copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates, polycarbonate plates; phenol resin plates, urea resin plates, unsaturated polyester resin plates Thermosetting resin plate such as polyurethane resin plate, epoxy resin plate and melamine resin plate; phenol resin, urea resin, tiredness Examples include so-called FRP boards, which are obtained by impregnating and hardening a resin such as polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin into glass fiber non-woven fabric, cloth, paper or other various fibrous base materials. These may be used alone or as a composite substrate in which two or more of these
  • the method of laminating on the adherend is not particularly limited, and examples thereof include a means for laminating via the primer layer described above and a means for laminating via an adhesive.
  • the adhesive may be appropriately selected from known adhesives depending on the type of the adherend. For example, polyvinyl acetate, urethane, acryl, urethane acryl (including copolymer) polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylonitrile rubber , Neoprene rubber, natural rubber and the like.
  • a heat-melting method, a heat-laminating method, a water-based adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot-melt adhesive, or the above-mentioned transparent adhesive layer is formed.
  • a method of laminating the base material, the pattern layer, and the transparent resin film using an adhesive or the like is used.
  • the step of forming an adhesive layer on the surface of the transparent resin film on which the picture layer is laminated, and the transparent layer through the adhesive layer It is preferable to have a step of bonding the functional resin film and the above-mentioned pattern layer.
  • Such a method for producing a decorative board of the present invention is also an aspect of the present invention.
  • embossing or the like is performed to form the uneven shape.
  • some concavo-convex shape is also formed on the surface opposite to the embossed surface (the surface on the side laminated on the pattern layer).
  • air trapping may occur, and the design may deteriorate.
  • a decorative board of the present invention since it has a step of forming an adhesive layer on the surface of the transparent resin film on the side having the pattern layer, it also adheres to the concave and convex portions on the side having the pattern layer.
  • the agent layer can be introduced, the above-mentioned air bite can be prevented from occurring, and the deterioration in designability can be suppressed.
  • Example 1 A transparent polypropylene film (thickness: 60 ⁇ m) is prepared, and a two-component curable urethane resin (thickness: 1 ⁇ m) using silica-added isocyanate as a curing agent is applied to one surface of the transparent polypropylene film to form a primer layer for a surface protective layer.
  • a transparent polypropylene resin (thickness: 200 ⁇ m) was extruded and laminated on the other surface of the transparent polypropylene film (the side on which the primer layer for the surface protective layer is not coated) by an extrusion heat lamination method.
  • a two-component curing type urethane resin (thickness 2 ⁇ m) having isocyanate as a curing agent to be an external haze layer was applied.
  • the urethane (meth) acrylate which is an electron beam curable resin, was applied to the coated surface of the primer layer for the surface protective layer by a gravure coating method so that the coating amount was 15 ⁇ m, an accelerating voltage of 165 keV using an electron irradiation device, An electron beam was irradiated under the condition of 5 Mrad to form a surface protective layer.
  • a two-component curing type polyester resin (thickness: 50 ⁇ m) having an isocyanate as a curing agent is applied to the side opposite to the side having the uneven shape of the obtained transparent resin film to form an adhesive layer, and the obtained transparency is obtained.
  • the side of the resin film opposite to the side having the uneven shape and the side of the base material provided with the pattern layer side were laminated with the adhesive layer interposed therebetween. After that, a pressure of 10 kg / m 2 was applied and curing was performed for 3 days in a room temperature environment.
  • DIRECT HASE METER manufactured by Toyo Seiki Co., Ltd.
  • Haze value of the entire sheet The haze value was measured by shining light from the surface side of the transparent resin film having the uneven shape, specifically, the side of the surface protective layer having the uneven shape in Example 1.
  • Haze value when the back surface is wet Pure water was dropped on the surface side of the transparent resin film having the external haze layer, and the PET film (Lumirror T60 manufactured by Toray Industries, Inc., 50 ⁇ m thick, haze value 0.1%) was exposed to air.
  • the haze value was obtained by stacking so as not to bite, and then irradiating light from the surface side of the transparent resin film having the uneven shape, specifically, the side of the surface protective layer having the uneven shape in Example 1.
  • Haze value of the external haze layer Calculated as a value obtained by subtracting the haze value when the back surface is wet from the haze value of the entire sheet.
  • Example 1 A transparent resin film was produced in the same manner as in Example 1 except that samples having different haze values of the outer haze layer were used as shown in Table 1. Then, the same evaluation as in Example 1 was performed.
  • Example 5 A polypropylene resin (thickness 60 ⁇ m) is prepared, and a primer agent is applied to one surface (the side to be laminated on the base material having a pattern layer) of the outer haze layer (thickness 2 ⁇ m, using isocyanate as a curing agent). Two-component curing type urethane resin) was formed. Polypropylene resin (thickness 60 ⁇ m) was extruded and laminated on the other surface of the polypropylene resin by a heat laminating method. Immediately thereafter, it was brought into contact with a metal roll whose temperature was 10 ° C.
  • a primer agent for the surface protective layer.
  • An ionizing radiation curable resin (coating amount: 15 ⁇ m) was applied on the surface by a gravure coating method, and then an electron beam was irradiated using an electron irradiation device under conditions of an acceleration voltage of 165 keV and 5 Mrad to form a surface protective layer.
  • the side having the surface protective layer was heated with an infrared non-contact type heater, and then embossing was performed by hot pressure to obtain a transparent resin film having an uneven shape.
  • a base having a pattern layer provided on the surface of the transparent resin film having the external haze layer by applying a two-component curing type polyester (thickness 50 ⁇ m) to form an adhesive layer and having a thickness of 2 ⁇ m by an inkjet printer. It laminated on the material (MDF (medium density fiberboard) thickness 3mm), and obtained the decorative board.
  • MDF medium density fiberboard
  • Example 6 A decorative board was produced in the same manner as in Example 5 except that the thickness of the outer haze layer was changed to 1 ⁇ m.
  • Example 7 A decorative board was produced in the same manner as in Example 5 except that the thickness of the outer haze layer was changed to 5 ⁇ m.
  • a polypropylene resin (thickness 60 ⁇ m) was prepared, and a primer agent (thickness 2 ⁇ m, two-component curable urethane resin having isocyanate as a curing agent) was applied to one surface of the polypropylene resin to form an external haze layer.
  • Polypropylene resin (thickness 60 ⁇ m) was extruded and laminated on the other surface of the polypropylene resin by a heat laminating method. Immediately after that, it was brought into contact with a metal roll at 50 ° C. for 0.5 seconds, then left in an environment of 25 ° C., and further cooled at 50 ° C./sec (slow cooling) to form a transparent external haze layer. A resinous layer was obtained.
  • a decorative board was produced in the same manner as in Example 5 except for the above.
  • Haze value (1) excluding the surface haze on the side opposite to the side laminated on the substrate of the transparent resin films obtained in Examples 5 to 7 and Reference Examples 2 to 3, and the side laminated on the substrate.
  • the haze value (2) excluding the surface haze and the surface haze on the side opposite to the side laminated on the substrate was measured by the following method.
  • the obtained sheet from the side of the transparent resin film having the uneven shape, more specifically, from the side of the PET film laminated on the side of the transparent resin film having the uneven shape, the DIRECT READING HAZE METER (Toyo Seiki Co., Ltd. Haze value of the PET film is excluded by measuring the haze value of the PET film, specifically, the haze value of the PET film is 1.5%, and the total haze value is 3%. ) Got.
  • the decorative board of the present invention is suitably used for interior fittings such as fittings and doors such as sliding doors, flooring materials, walls, ceilings, and various decorative molded bodies.

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Abstract

本発明は、基材に設けられた絵柄層に積層したときに密着状態を目視で確認できる透明性樹脂フィルム、並びに、該透明性樹脂フィルムを用いてなる化粧板及び該化粧板の製造方法を提供する。 本発明は、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、上記透明性樹脂フィルムは、少なくとも、熱可塑性樹脂層と、上記絵柄層に積層される側に外部ヘイズ層とを有することを特徴とする透明性樹脂フィルムに関する。

Description

透明性樹脂フィルム、化粧板及び化粧板の製造方法
本発明は、透明性樹脂フィルム、該透明性樹脂フィルムを用いてなる化粧板及び該化粧板の製造方法に関する。
近年、インクジェットプリンターを用いたインクジェット印刷法の普及により、建材や加飾成形品等に用いられている化粧シートにおいても、多品種・小ロットにも対応できることや絵柄層として複雑な柄(文字、数字そして図形等)を印刷することが可能となった。更に、インクジェット印刷法は印刷する基材がフィルムに限らず、平板や凹凸や曲面を備えた基材に対しても印刷が可能というメリットがある。
しかし、通常、インクジェット印刷法で印刷された絵柄層は基材の最表面にあることから、耐傷性や耐汚染性及び耐候性等の表面性能が不十分であり、その絵柄層を保護するために透明性樹脂フィルムを絵柄層の表面に積層する必要があった。
このような透明樹脂フィルムとして、例えば、特許文献1には、トリアジン系紫外線吸収剤とヒンダードアミン系光安定剤とを含む透明ポリプロピレンの一方の面に保護層、他方の面に粘着層を設けたオーバーラミネートフィルムが開示されている。
しかしながら、従来の透明性樹脂フィルムは、基材に設けられた絵柄層と積層した際、上記基材に設けられた絵柄層と透明性樹脂フィルムとの間に空気を噛んでしまっている場合であっても、透明性樹脂フィルムの表面の艶の変化量も少ないため、目視では空気を噛んでいるか否かの判断がしにくく、また、空気を噛んでしまっている場合、絵柄層と透明性樹脂フィルムとの間の密着力の低下が問題となることがあった。
特開2005-120255号公報
本発明は、基材に設けられた絵柄層に積層したときに密着状態を目視で確認できる透明性樹脂フィルム、並びに、該透明性樹脂フィルムを用いてなる化粧板及び該化粧板の製造方法を提供することを目的とする。
本発明者らは、上述した課題を解決するため鋭意検討した結果、透明性樹脂フィルムに関し、基材の絵柄層に積層される側の面に外部ヘイズ層を設けることで、基材の絵柄層の表面に透明性樹脂フィルムを積層した際に、空気を噛んでいるか否かを目視にて容易に判断でき、空気を噛んでいることで上記絵柄層との密着力が低下しているものを除外することで、上記絵柄層との密着性を優れたものとすることが容易な透明性樹脂フィルムとすることができることを見出し、本発明を完成するに至った。
本発明は、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、上記透明性樹脂フィルムは、少なくとも、熱可塑性樹脂層と、上記絵柄層に積層される側に外部ヘイズ層とを有することを特徴とする透明性樹脂フィルムである。
上記外部ヘイズ層のヘイズ値が4%以上、100%未満であることが好ましい。
上記外部ヘイズ層の熱可塑性樹脂層側と反対側に純水層を介してヘイズ値が0.1%以下のポリエチレンテレフタレートフィルムを貼り付け、前記熱可塑性樹脂層側から測定した裏面が濡れた状態でのヘイズ値が90%以下であることが好ましい。
上記外部ヘイズ層の厚みが0.5μm以上、20μm以下であることが好ましい。
上記透明性樹脂フィルムは、上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、上記絵柄層に積層される側と反対側の表面ヘイズを除いたヘイズ値であるヘイズ値(1)が、70%以上であり、上記絵柄層に積層される側の表面ヘイズと、上記絵柄層に積層される側と反対側の表面ヘイズとを除いたヘイズ値であるヘイズ値(2)が、70%以下であることが好ましい。
上記熱可塑性樹脂層の上記絵柄層に積層される側と反対側に、表面保護層を有することが好ましい。
また、本発明は、厚み方向において順に、基材と、絵柄層と、本発明の透明性樹脂フィルムとを備えることを特徴とする化粧板でもある。
本発明は、本発明の化粧板の製造方法であって、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化粧板の製造方法でもある。
本発明の透明性樹脂フィルムは、基材の絵柄層に積層される側の面に外部ヘイズ層を有するため、基材の絵柄層の表面に透明性樹脂フィルムを積層した際に、空気を噛んでいるか否かを目視にて容易に判断でき、空気を噛んでいることで上記絵柄層との密着力が低下しているものを除外することで、上記絵柄層との密着性が優れたものとすることが容易となる。
このような本発明の透明性樹脂フィルムを基材の絵柄層表面に積層してなる本発明の化粧板は、絵柄層と透明性樹脂フィルムとの間に空気を噛んでいない状態に容易にでき、これらの密着力を容易に優れたものとすることができる。
本発明の透明性樹脂フィルムの好ましい一例の断面を示す模式図である。 本発明の透明性樹脂フィルムの好ましい別の一例の断面を示す模式図である。 本発明の化粧板の好ましい一例の断面を示す模式図である。
<透明性樹脂フィルム>
まずは、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の好ましい一例について、図面を用いて説明する。
図1に示すように本発明の透明性樹脂フィルム10は、少なくとも、熱可塑性樹脂層11と外部ヘイズ層12とを有する。
(熱可塑性樹脂層)
上記熱可塑性樹脂層を構成する熱可塑性樹脂としては、以下の樹脂を1種以上含むものであり、例えば、ポリエチレン(低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン)、エチレン-αオレフィン共重合体、ポリプロピレン、ポリブテン、ポリメチルペンテン、エチレン-プロピレン共重合体、プロピレン-ブテン共重合体、エチレン-酢酸ビニル共重合体、エチレン-酢酸ビニル共重合体ケン化物、オレフィン系熱可塑性エラストマー、又は、これらの混合物等のオレフィン樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナレフタレート、エチレングリコール-テレフタル酸-イソフタール酸共重合体、テレフタル酸-エチレングリコール-1,4シクロヘキサンジメタノール共重合体、ポリエステル系熱可塑性エラストマー等のポリエステル樹脂、ポリメチル(メタ)アクリレート、メチル(メタ)アクリレート-ブチル(メタ)アクリレート共重合体、メチル(メタ)アクリレート-スチレン共重合体等のアクリル樹脂、ナイロン-6、ナイロン-66等のポリアミド系熱可塑性樹脂、ポリカーボネート樹脂、ポリ塩化ビニル、ポリスチレン、アイオノマー等が挙げられる。なかでも、引張強度が高く、耐薬品性能に優れ、生産工程面で優れていることからポリプロピレンが好適に用いられる。
なお、本明細書において、(メタ)アクリレートとは、アクリレート又はメタクリレートを意味する。
上記熱可塑性樹脂層は、未延伸であってもよいが必要に応じて1軸延伸又は2軸延伸されたものであってもよい。
また、上記熱可塑性樹脂層の厚みとしては特に限定されないが、好ましい下限は20μm、好ましい上限は500μmであり、より好ましい下限は60μm、より好ましい上限は420μmである。
上記熱可塑性樹脂層の厚みが20μm未満であると、引張強度が不十分となり上記絵柄層の表面を保護できないことがあり、500μmを超えると、本発明の透明性樹脂フィルム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。
上記熱可塑性樹脂層は、基材に備えられた絵柄層が可視できれば特に限定されず、着色されていてもよい。この場合は、上記非ハロゲン系熱可塑性樹脂に着色剤を添加すればよい。着色剤としては、後述する絵柄層で用いる顔料又は染料が使用できる。
上記熱可塑性樹脂層には、充填剤、艶消し剤、発泡剤、難燃剤、滑剤、帯電防止剤、酸化防止剤、紫外線吸収剤、光安定化剤、ラジカル捕捉剤、軟質成分(例えば、ゴム)等の各種の添加剤を含めてもよい。
上記熱可塑性樹脂層が2層以上の構成である場合、透明性接着剤層を介して積層されていても良いし、熱ラミネート方式により積層されていても良い。
接着剤が不要となり、接着剤の劣化による剥離等の問題が生じないことから、熱ラミネート方式により積層されていることが好ましい。
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。
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る。
上記透明性接着剤層は、乾燥後の厚みが0.1~30μm程度が好ましく、1~5μm程度がより好ましい。
上記熱ラミネート方式により、2層以上の上記熱可塑性樹脂層を積層した後は、急冷することにより、ヘイズ値を調整することもできる。
ここで急冷とは、透明性樹脂フィルムが、200℃/秒以上で冷却されることを意味する。
上記急冷をする方法としては、熱ラミネート方式により、ラミネートされた直後10℃以下に冷やされた金属ロール数秒間触れさせる方法等が挙げられる。
上記急冷の速度としては、230℃/秒で冷却することが好ましく、250℃/秒で冷却することがより好ましい。
上記熱可塑性樹脂層の上記外部ヘイズ層が設けられた側の面(以下、裏面ともいう)と反対側の表面(以下、表面ともいう)は、平滑面であってもよく凹凸形状を有していてもよい。
上記表面が平滑面であることで、基材の一方の面上に積層された絵柄層をより鮮明に映し出すことができる。
なお、上記平滑面とは、JIS B 0601(1982)に規定される中心線平均粗さRaが2.0μm以下である面を意味する。
なお、上記「表面」は、透明性樹脂フィルムの最表面(絵柄層に積層される側と反対側)を意味し、透明性樹脂フィルムが後述する表面保護層を有する場合は、表面保護層を有する側の最表面を意味する。
また、上記表面が凹凸形状を有することで本発明の透明性樹脂フィルムに意匠感を出すことができ、本発明の透明性樹脂フィルムを用いてなる化粧板の意匠性をより優れたものとすることができる。
また、形成される凹凸形状の深さとしては特に限定されないが、例えば、JIS B 0601(1982)に規定される中心線平均粗さRaが5~20μm範囲内になるように適宜調整することが好ましい。
上記凹凸形状は、JIS B 0601(2001)で定義される最大高さRzが20μm以上、200μm以下であることが好ましい。
本発明の透明性樹脂フィルムは、上記凹凸形状を有することにより、意匠性をより好適に向上することができる。
一方、上記最大高さRzが20μm未満であると、意匠性を十分に付与できないことがあり、200μmを超えると、上記凹凸形状の賦形性が低下することがある。
上記最大高さRzは、50μm以上、180μm以下であることが好ましく、70μm以上、150μm以下であることがより好ましい。
なお、本明細書において、JIS B 0601(1982)に規定される中心線平均粗さRa、及び、JIS B 0601(2001)で定義される最大高さRz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木目導管やヘアライン調の場合には、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最大高さ(Rz)とする。
その際、測定箇所は凹凸形状があるところを選定し測定する。
上記熱可塑性樹脂層の表面に凹凸形状を形成する方法としては特に限定されず、例えば、熱によるエンボス加工、賦形シートによって熱可塑性樹脂層に凹凸形状を転写させる方法等が挙げられる。
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、エンボス加工の柄模様としては、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く、例えば、シート温度120℃~160℃、1.0~4.0MPaにて凹凸パターンを転写すればよい。
なお、透明性樹脂フィルムにエンボス加工を施す場合は、後述する表面保護層を形成した後でもよいし、表面保護層を形成する前でもよい。
例えば、具体的な態様として、1)熱可塑性樹脂層を形成した後、表面保護層を形成し、最後にエンボス加工を施してもよい。また、別の具体的態様として、2)熱可塑性樹脂層を形成した後、エンボス加工を施し、最後に表面保護層を形成してもよい。また、さらに別の具体的態様として、3)熱可塑性樹脂層を形成すると同時にエンボス加工を施した後、最後に表面保護層を形成してもよい。
(表面保護層)
図2に示すように、本発明の透明性樹脂フィルム10は、熱可塑性樹脂層11の外部ヘイズ層12と反対側の表面には、更に表面保護層用プライマー層13を介して表面保護層14が設けられていてもよい。
上記表面保護層を有することで本発明の透明性樹脂フィルムの耐久性(耐傷性、耐汚染性、耐候性等)がより優れたものとなり、より好適に絵柄層の表面保護が可能となり、本発明の透明性樹脂フィルム自体の傷付きによる意匠性の低下を好適に防止できる。
なお、上記表面保護層は、単一の層構成であってもよく、同一又は異なる材料からなる複数の層構成であってもよい。
上記表面保護層としては特に限定されないが、例えば、2液硬化型樹脂や電離放射線硬化性樹脂組成物の架橋硬化物からなるものが挙げられ、該架橋硬化物は、透明であることが好ましく、透明である限り後述する絵柄層が視認できる範囲であれば、半透明でも着色されていてもよい。
上記2液硬化型樹脂としては、例えば、2液硬化型ウレタン樹脂、2液硬化型ポリエステル樹脂、2液硬化型エポキシ樹脂などが挙げられる。
上記電離放射線硬化性樹脂組成物としては、例えば、分子中にラジカル重合性不飽和結合又はカチオン重合性官能基を有するオリゴマー(以下、所謂プレポリマー、マクロモノマー等も包含する)及び/又は分子中にラジカル重合性不飽和結合又はカチオン重合性官能基を有するモノマーが好ましく用いられる。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。
上記オリゴマー又はモノマーとしては、例えば、分子中に(メタ)アクリロイル基、(メタ)アクリロイルオキシ基等のラジカル重合性不飽和基、エポキシ基等のカチオン重合性官能基等を有する化合物が挙げられる。これらオリゴマー、モノマーは、単独で用いるか、或いは複数種混合して用いることができる。なお、本明細書において、上記(メタ)アクリロイル基とは、アクリロイル基又はメタクリロイル基を意味する。
上記分子中にラジカル重合性不飽和基を有するオリゴマーとしては、例えば、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、メラミン(メタ)アクリレート、トリアジン(メタ)アクリレート等のオリゴマーが好ましく使用でき、ウレタン(メタ)アクリレートオリゴマーがさらに好ましい。分子量としては、通常250~10万程度のものが用いられる。
また、上記分子中にラジカル重合性不飽和基を有するモノマーとしては、例えば、多官能モノマーが好ましく、多官能(メタ)アクリレートがより好ましい。
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。
本発明において、上述の電離放射線硬化性樹脂組成物がウレタンアクリレートオリゴマー及び多官能モノマーからなる電離放射線硬化性樹脂成分を含むことがさらに好ましく、電離放射線硬化性樹脂成分として、ウレタンアクリレートオリゴマー/多官能モノマー(質量比)が6/4~9/1であることが特に好ましい。この質量比の範囲であれば、耐擦傷性により優れたものにできる。
なお、必要に応じ、上記電離放射線硬化性樹脂成分に加えて、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性樹脂組成物を紫外線にて架橋させる場合、電離放射線硬化性樹脂組成物に光重合開始剤を添加することが好ましい。
上記電離放射線硬化性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性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、電離放射線硬化性樹脂成分100質量部に対して0.1~10質量部程度である。
なお、上記電離放射線硬化性樹脂組成物には、更に必要に応じて各種添加剤を加えても良い。これらの添加剤としては、例えば、ウレタン樹脂、ポリビニルアセタール樹脂、ポリエステル樹脂、ポリオレフィン樹脂、スチレン系樹脂、ポリアミド樹脂、ポリカーボネート樹脂、アセタール樹脂、塩化ビニル-酢酸ビニル共重合体、酢酸ビニル樹脂、アクリル樹脂、セルロース系樹脂等の熱可塑性樹脂、シリコーン樹脂、ワックス、弗素樹脂等の滑剤、ベンゾトリアゾール、ベンゾフェノン等の紫外線吸収剤、ヒンダードアミン系ラジカル捕捉剤等の光安定剤、染料、顔料等の着色剤等である。
なお、電離放射線の電子線源としては、例えば、コッククロフトワルトン型、バンデグラフト型、共振変圧器型、絶縁コア変圧器型、或いは、直線型、ダイナミトロン型、高周波型等の各種電子線加速器を用い、70~1000keVのエネルギーをもつ電子を照射するものが使用できる。また、電子線の照射線量は、例えば、1~10Mrad程度であることが好ましい。
また、上記電離放射線の紫外線源としては、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が使用でき、上記紫外線の波長としては通常190~380nmの波長域が主として用いられる。
(表面保護層用プライマー層)
上記表面保護層用プライマー層は、バインダー樹脂を含有することが好ましい。
上記表面保護層用プライマー層は透明であることが好ましく、透明である限り絵柄層が視認できる範囲内であれば、半透明であっても着色されていてもよい。
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(アクリル変性ウレタン樹脂)、アクリル-ウレタン共重合体樹脂(ブロック共重合体等)、セルロース樹脂、ウレタン-セルロース系樹脂(例えば、ウレタンと硝化綿の混合物にヘキサメチレンジイソシアネートを添加してなる樹脂)、ポリエステル樹脂、塩化ビニル-酢酸ビニル共重合体樹脂等が挙げられる。上述した表面保護層の電離放射線硬化性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、表面保護層との密着性や生産時の効率からウレタン樹脂が好ましい。
上記表面保護層用プライマー層は、厚みが0.5μm以上、10μm以下であることが好ましい。0.5μm以上であれば、本発明の透明性樹脂フィルムと後述する絵柄層との密着性を好適に確保でき、10μm以下であれば、本発明の透明性樹脂フィルムが厚くなり過ぎず、十分な透明性が得られ、化粧板の意匠性が好適に確保できる。また、製膜の際のブロッキングも抑制できる。
なお、ブロッキングとは透明性樹脂フィルムを製膜や接着用プライマー等を塗工し、それをロール状に巻き上げ、それを巻き解く際にフィルム同士が離れにくくなる現象である。更に、上記表面保護層用プライマー層は、シリカ等の無機微粒子を含んでいてもよい。
また、上記表面保護層用プライマー層には、必要に応じて、添加剤を配合してもよい。添加剤としては、例えば、炭酸カルシウム、クレー等の充填剤、水酸化マグネシウム等の難燃剤、酸化防止剤、滑剤、発泡剤、紫外線吸収剤、光安定剤などが挙げられる。添加剤の配合量は、製品特性に応じて適宜設定できる。
(外部ヘイズ層)
本発明の透明性樹脂フィルムは、外部ヘイズ層を有する。
上記外部ヘイズ層は、後述する基材の一方の面上に積層された絵柄層の表面を保護するために、上記熱可塑性樹脂層の裏面に積層されている。
本発明の透明性樹脂フィルムは、上記外部ヘイズ層のヘイズ値が4%以上、100%未満であることが好ましい。上記ヘイズ値が4%未満であると、本発明の透明性樹脂フィルムを上記絵柄層表面に積層したときに空気噛みを目視で判別できないことがあり、また、密着性も不十分となることがある。上記外部ヘイズ層のヘイズ値のより好ましい下限は5%、更に好ましい下限は6%である。
上記外部ヘイズ層のヘイズ値は、透明性樹脂フィルム全体のヘイズから裏面が濡れた状態でのヘイズを引いた値である。
上記透明性樹脂フィルム全体のヘイズは、例えば、外部ヘイズ層の表面側から又は透明樹脂フィルムの表面側から光を当てて公知のヘイズメータを用いて測定することができる。
上記裏面が濡れた状態でのヘイズは、透明性樹脂フィルムの裏面側に純水を介してヘイズ値が0.1%以下のPETを貼り付けた状態で、上記透明性樹脂フィルムの表面側から光を当てて公知のヘイズメータを用いて測定することができる。このようにすることで透明性樹脂フィルムから外部ヘイズ層のヘイズ値を除いたヘイズ値を算出することが出来るためである。
本発明の透明性樹脂フィルムにおいて、上記外部ヘイズ層の熱可塑性樹脂層側と反対側に純水層を介してヘイズが0.1%以下のポリエチレンテレフタレートフィルムを貼り付け、上記熱可塑性樹脂層側から測定した裏面が濡れた状態でのヘイズ値が90%以下であることが好ましい。
上記熱可塑性樹脂層側から測定した裏面が濡れた状態でのヘイズ値が90%を超えると、本発明の透明性樹脂フィルムの透明性が低下して化粧板としたときに絵柄層の視認性に劣ることがある。
上記裏面が濡れた状態でのヘイズ値のより好ましい上限は80%であり、更に好ましい上限は60%である。
上記外部ヘイズ層を構成する材料としては上記絵柄層との密着をより良好にするために用いられる材料であり、例えば、ウレタン樹脂、アクリル樹脂、ウレタン-アクリル樹脂、ウレタン-アクリル共重合体樹脂、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。
上記外部ヘイズ層は、厚みが0.5μm以上、20μm以下であることが好ましい。0.5μm未満であると、基材と透明性樹脂フィルムとの密着性が不十分であり、一方、20μmを超えると、透明性樹脂フィルムの作製時にロール状にするとフィルムの表裏が接することでブロッキングが発生してしまうことがある。上記外部ヘイズ層の厚みのより好ましい下限は0.8μm、より好ましい上限は15μmであり、更に好ましい下限は1μm、更に好ましい上限は10μmである。
上記裏面が濡れた状態でのヘイズ値を上記範囲内にする方法としては、例えば、熱可塑性樹脂層に含まれる添加剤量を調整する方法や熱可塑性樹脂層の厚みを薄膜化する方法等が考えられる。
上記外部ヘイズ層は、上記熱可塑性樹脂層との密着性をより強固にするために、熱可塑性樹脂層の外部ヘイズ層を設ける面にコロナ放電処理やプラズマ処理等の表面処理を施してもよい。上記表面処理の方法・条件は、公知の方法に従って実施すれば良い。
更に外部ヘイズ層と基材層との間にプライマー層を形成したりして密着性を高めてもよい。
なお、上記外部ヘイズ層は基材層や熱可塑性樹脂層との密着を良好にするためのプライマー層としての機能を有してもよい。上記プライマー層としては、上述した表面保護層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。
上記外部ヘイズ層は、熱可塑性樹脂層側と反対側の面に上記熱可塑性樹脂層と同様の層を単層又は複数層有していてもよい。
また、上記外部ヘイズ層には、必要に応じて、添加剤を配合してもよい。添加剤としては、例えば、炭酸カルシウム、クレー等の充填剤、水酸化マグネシウム等の難燃剤、酸化防止剤、滑剤、発泡剤、紫外線吸収剤、光安定剤などが挙げられる。添加剤の配合量は、製品特性に応じて適宜設定できる。
(透明性樹脂フィルムのヘイズ値)
本発明の透明性樹脂フィルムは、基材に積層される側と反対側の表面ヘイズを除いたヘイズ値(以下、ヘイズ値(1)ともいう)が70%以上であることが好ましい。
本発明の透明性樹脂フィルムが、このようなヘイズを有することにより、熱吸収率を高めることができるので、凹凸形状の賦形性に優れる。
通常、エンボス加工等により形成された凹凸形状は、熱や時間の経過等により消失してしまうが、上記ヘイズ値(1)が所定の範囲であることにより、このような凹凸形状の消失を抑制することができる。
上記ヘイズ値(1)は、75%以上であることがより好ましく、80%以上であることが更に好ましい。
なお、本明細書において、上記ヘイズとは、DIRECT READING HAZE METER(東洋精機社製)を用いて測定される値である。
上記ヘイズ値(1)は、下記の方法により測定することができる。
すなわち、透明性樹脂フィルム、純水、及び、PETフィルム(ヘイズ値が3%以下)が、この順に積層されたシートを作製する。
このとき、透明性樹脂フィルムの凹凸形状を有する側に、上記純水が積層されるようにする。
得られたシートについて、透明性樹脂フィルムの凹凸形状を有する側、より具体的には透明性樹脂フィルムの凹凸形状を有する側に積層されたPETフィルムの側から、DIRECT READING HAZE METER(東洋精機社製)を用いてヘイズ値を測定し、上記PETフィルムのヘイズ値を除く、具体的には、PETフィルムのへイズ値(例えば3%)を引くことにより得ることができる。
本発明の透明性樹脂フィルムは、基材に積層される側の表面ヘイズと、基材に積層される側と反対側の表面ヘイズとを除いたヘイズ値(以下、ヘイズ値(2)ともいう)が、70%以下であることが好ましい。
本発明の透明性樹脂フィルムは、このようなヘイズを有することにより、後述する絵柄層に形成された柄を明瞭に見ることができるので、意匠性に優れる。
上記ヘイズ値(2)は、65%以下であることがより好ましく、60%以下であることが更に好ましい。 
上記ヘイズ値(2)は、下記の方法により測定することができる。
すなわち、PETフィルム(ヘイズ値が3%以下)、純水、透明性樹脂フィルム、純水、及び、PETフィルム(ヘイズ値が3%以下)が、この順に積層されたシートを作製する。
得られたシートについて、透明性樹脂フィルムの凹凸形状を有する側、より具体的には透明性樹脂フィルムの凹凸形状を有する側に積層されたPETフィルムの側から、DIRECT READING HAZE METER(東洋精機社製)を用いてヘイズ値を測定し、上記PETフィルムのヘイズ値を除く、具体的には、それぞれのPETフィルム(例えば、PETフィルムのへイズ値それぞれ3%、合計で6%)を引くことにより得ることができる。
(透明性樹脂フィルムの製造方法)
本発明の透明性樹脂フィルムの製造方法としては、特に限定されず、上述した各層を上記透明性接着剤層や表面保護層用プライマー層等を介して積層させる方法や、熱ラミネート方式により積層する方法等が挙げられる。
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>
本発明の透明性樹脂フィルムは、上記絵柄層を保護するために用いられ、基材の絵柄層に積層される側の面に外部ヘイズ層を有するため、基材の絵柄層の表面に透明性樹脂フィルムを積層した際に、空気を噛んでいるか否かを目視にて容易に判断でき、上記絵柄層との密着性を優れたものとすることが容易となる。
このような厚み方向において順に、基材と、絵柄層と、本発明の透明性樹脂フィルムとを備えることを特徴とする化粧板もまた、本発明の一態様である。
次に、本発明の化粧板の好ましい一例について、図3を用いて説明する。
本発明の化粧板20は、基材25の一方の面上に絵柄層24が積層され、絵柄層24の基材25を有する側と反対側に本発明の透明性樹脂フィルム10が積層されている。
また、絵柄層24と、本発明の透明性樹脂フィルム10との密着性をより強固にする観点から、接着剤層23を有することが好ましい。
以下、本発明の化粧板の各構成について説明する。
(基材)
上記基材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。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(ABS樹脂)、アクリロニトリル-スチレン共重合体などの熱可塑性樹脂の単体及び共重合体、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、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。
また、上記木質材料としては、例えば、杉、檜、欅、松、ラワン、チーク、メラピー等の各種素材等が挙げられ、また、芯材としては、これらの素材から作られた突板、木材単板、木材合板(LVLを含む)、パーティクルボード、中密度繊維板(MDF)、高密度繊維板(HDF)、集成材等のいずれか、ないし、これらを適宜積層した積層材であってもよい。
上記金属材料としては、例えば、鉄等が挙げられる。
また、上記基材は、無機化合物を含んでいてもよい。
また、上記基材が複数の熱可塑性樹脂層を有する場合、該複数の熱可塑性樹脂層を形成する樹脂の種類は同じであっても異なっていてもよく、また複数の熱可塑性樹脂層の厚みは同じであっても異なっていてもよい。
本発明において、上記基材は、中空構造であっていてもよいし、基材の一部にスリット溝や貫通穴を設けてもよいし、上記材料を組み合わせた枠状のものでもよい。
上記基材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。
なお基材は平板以外の略板状であり、凹凸や曲面を備えているものも含まれる。
(絵柄層)
また、上記基材に備わる絵柄層は、本発明の透明性樹脂フィルムを用いてなる本発明の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。
上記隠蔽層を設けることにより、上述した基材が着色していたり色ムラがあったりする場合に、意図した色彩を与えて表面の色を整えることができる。
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、パッチワークなどの模様を化粧シート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。
上記絵柄層に用いられるインキ組成物としては、バインダー樹脂に顔料、染料などの着色剤、体質顔料、溶剤、安定剤、可塑剤、触媒、硬化剤などを適宜混合したものが使用される。該バインダー樹脂としては特に制限はなく、例えば、ウレタン樹脂、塩化ビニル/酢酸ビニル共重合体樹脂、塩化ビニル/酢酸ビニル/アクリル共重合体樹脂、アクリル樹脂、ポリエステル樹脂、ニトロセルロース樹脂などが好ましく挙げられる。上記バインダー樹脂としてはこれらの中から任意のものを、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。
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。
上記絵柄層の厚みとしては特に限定されず、例えば、0.1μm以上が好ましく、0.5μm以上600μm以下がより好ましい。上記絵柄層の厚みが上記範囲内にあれば、本発明の化粧板に優れた意匠を付与することができ、また隠蔽性を付与することができる。
なお、突板等のように予め基材自体に意匠性を備えているような基材自体の意匠を生かしたい場合には、基材自体が絵柄層を兼ねるため別途絵柄層を設けなくてもよい。
本発明の透明性樹脂フィルムは、上記外部へイズ層が上述した基材の一方の面上に積層された絵柄層の表面に積層され、該絵柄層の表面を保護するために用いられる。
このような厚み方向において順に、基材と、絵柄層と、本発明の透明性樹脂フィルムとを備えることを特徴とする化粧板もまた、本発明の一つである。
本発明の化粧板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以下がより好ましい。
本発明の化粧板は、必要に応じて、さらにバッカー層等を有していてもよい。その際、被着材は透明性接着剤層、プライマー層、バッカー層等の裏側に設けてもよい。
上記透明性接着剤層及び上記プライマー層は、上述した透明性樹脂フィルム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。
(バッカー層)
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が挙げられ、上記基材最下層(上記透明性樹脂フィルムが積層される側と反対側)に有することが好ましい。
上記基材が上記バッカー層を有することにより、化粧板の耐傷性、耐衝撃性がより一層向上することができる。
上記合成樹脂バッカー層を構成する樹脂としては、例えば、ポリプロピレン、エチレン-ビニルアルコール共重合体、ポリエチレン、ポリメチルペンテン、ポリエチレンテレフタレート、耐熱性の高いポリアルキレンテレフタレート〔例えば、エチレングリコールの一部を1,4-シクロヘキサンジメタノールやジエチレングリコール等で置換したポリエチレンテレフタレートである、いわゆる商品名PET-G(イーストマンケミカルカンパニー社製)〕、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレンナフタレート-イソフタレート共重合体、非晶性ポリエステル(A-PET)、ポリカーボネート、ポリアリレート、ポリイミド、ポリスチレン、ポリアミド、ABS等が挙げられる。これらの樹脂は単独又は2種以上で使用できる。
上記合成樹脂バッカー層は、中空ビーズを含有してもよい。
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。
上記合成樹脂バッカー層の厚みは特に限定されないが、例えば、100~600μmが好ましく、150~450μmがより好ましい。
上記合成樹脂バッカー層を形成する方法としては、カレンダー成形、溶融樹脂の押出し成形等が挙げられる。なかでも溶融樹脂の押出し成形が好適であり、例えば、Tダイを用いた押出し成形がより好適である。
上記発泡樹脂バッカー層は、上記合成樹脂バッカー層よりも更に下層(凹凸形状を有する側と反対側)に有していてもよい。
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。
(支持体)
上記基材は、支持体であってもよい。
上記支持体としては特に限定されず、各種の紙類、プラスチックフィルム、木材等の木質系の板、窯業系素材等を用途に応じて適宜選択することができる。これらの材料はそれぞれ単独で使用してもよいが、紙同士の複合体や紙とプラスチックフィルムの複合体等、任意の組み合わせによる積層体であってもよい。
上記紙類としては、薄葉紙、クラフト紙、チタン紙等が挙げられる。これらの紙基材は、紙基材の繊維間ないしは他層と紙基材との層間強度を強化したり、ケバ立ち防止のため、これら紙基材に、更に、アクリル樹脂、スチレンブタジエンゴム、メラミン樹脂、ウレタン樹脂等の樹脂を添加(抄造後樹脂含浸、又は抄造時に内填)させたものでもよい。例えば、紙間強化紙、樹脂含浸紙等である。
これらの他、リンター紙、板紙、石膏ボード用原紙、又は紙の表面に塩化ビニル樹脂層を設けたビニル壁紙原反等、建材分野で使われることの多い各種紙が挙げられる。
さらには、事務分野や通常の印刷、包装等に用いられるコート紙、アート紙、硫酸紙、グラシン紙、パーチメント紙、パラフィン紙、又は和紙等を用いることもできる。また、これらの紙とは区別されるが、紙に似た外観と性状を持つ各種繊維の織布や不織布も基材として使用することができる。各種繊維としてはガラス繊維、石綿繊維、チタン酸カリウム繊維、アルミナ繊維、シリカ繊維、若しくは炭素繊維等の無機質繊維、又はポリエステル繊維、アクリル繊維、若しくはビニロン繊維等の合成樹脂繊維が挙げられる。
なお、上記紙類に熱硬化型樹脂を含浸させる場合には、従来より公知の熱硬化型樹脂を広く使用することができる。熱硬化型樹脂として、例えば、不飽和ポリエステル樹脂、ポリウレタン樹脂(2液硬化型ポリウレタンも含む)、エポキシ樹脂、アミノアルキッド樹脂、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、グアナミン樹脂、メラミン-尿素共縮合樹脂、珪素樹脂、ポリシロキサン樹脂等が挙げられる。
このように、上記紙類に熱硬化型樹脂を含浸して得られた層を熱硬化型樹脂層ともいう。そして、その熱硬化型樹脂が最終的に表面保護層としての役割も担う場合もある。
上記熱硬化型樹脂層を形成する方法としては、例えば、上記支持体が多孔質基材を有する場合、多孔質基材に上記熱硬化型樹脂を含浸させる方法が挙げられる。
含浸は、上記の熱硬化型樹脂を、多孔質基材のおもて側、裏側、のいずれか若しくは両方から供給することにより行うことができる。この方法は特に限定されず、例えば、熱硬化型樹脂を入れた浴槽に多孔質基材の離型層が形成されている面又はその反対の面から浸漬させる方法;キスコーター、コンマコーター等のコーターにより熱硬化型樹脂を多孔性基材の離型層が形成されている面、その反対の面、又はこれらの両面に塗布する方法;スプレー装置、シャワー装置等により熱硬化型樹脂を多孔性基材の離型層が形成されている面、その反対の面、又はこれらの両面に吹き付ける方法、等が挙げられる。
上記プラスチックフィルムを構成する樹脂の具体例としては、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、フェノール樹脂、ポリビニルアルコール、エチレン-ビニルアルコール共重合体等のビニル系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂、ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリメタクリル酸エチル等のアクリル樹脂、ポリスチレン、アクリロニトリル-ブタジエン-スチレン共重合体(ABS樹脂)、三酢酸セルロース、ポリカーボネート等が挙げられる。これらの中でも、耐候性、耐水性等の各種物性、印刷適性、成形加工適性、価格等の観点からポリオレフィン系樹脂、塩化ビニル樹脂、ポリエステル樹脂、或いはアクリル樹脂が好ましい。
上記支持体の厚みは特に制限はないが、支持体がプラスチックフィルムの場合、20~200μmが好ましく、40~160μmがより好ましく、40~100μmが更に好ましい。
上記支持体が紙類の場合、坪量は、通常20~150g/mが好ましく、30~100g/mがより好ましい。
上記支持体の形状は平板状のものに限られず、立体形状等の特殊形状であってもよい。
上記支持体上には、支持体上に設けられる層との密着性を向上させるために、片面又は両面に、物理的処理又は化学的表面処理等の易接着処理を行ってもよい。
(フェノール樹脂含浸紙)
上記化粧板は、必要に応じて、フェノール樹脂含浸紙が積層されていてもよい。
上記フェノール樹脂含浸紙は、多孔質基材の、耐摩耗層及び離型層が形成されている側とは反対側の面に積層するとよい。
上記フェノール樹脂含浸紙とは、一般に、コア紙として坪量150~250g/m程度のクラフト紙にフェノール樹脂を含浸率45~60%程度となるように含浸し、100~140℃程度で乾燥させることにより製造された紙である。フェノール樹脂含浸紙には、市販品を使用することができる。フェノール樹脂含浸紙を積層する際には、必要に応じて、多孔質基材の裏面にコロナ放電処理を施したり、上述したプライマー層を塗布することにより裏面プライマー層を形成したりしてもよい。
(シーラー層)
上記支持体として、紙類等の含浸性のある基材を用いる場合、支持体と絵柄層との間等にシーラー層を有していてもよい。
上記シーラー層中には、熱硬化性樹脂組成物又は電離放射線硬化型樹脂組成物等の硬化性樹脂組成物の硬化物を含むことが好ましく、その中でも熱硬化性樹脂組成物の硬化物を含むことがより好ましい。
上記硬化性樹脂組成物の硬化物の含有量はシーラー層の全固形分の50質量%以上であることが好ましく、65~95質量%であることがより好ましい。
上記シーラー層の熱硬化性樹脂組成物及び電離放射線硬化型樹脂組成物は、上記表面保護層で例示したものと同様のものが挙げられる。また、熱硬化性樹脂組成物としては、ポリオールとイソシアネートとの2液硬化性樹脂が好ましく、アクリルポリオールとヘキサメチレンジイソシアネートとの2液硬化性樹脂がより好ましい。
上記シーラー層中には、乾燥適性及び粘度調整の観点から粒子を含むことが好ましい。粒子の含有量はシーラー層の全固形分の5~50質量%であることが好ましく、5~35質量%であることがより好ましい。
上記シーラー層の粒子は、無機粒子が好ましく、その中でもシリカが好ましい。
該粒子は、平均粒子径が0.1~2.0μmであることが好ましく、0.2~1.5μmであることがより好ましい。
<被着材>
本発明の化粧板は、凹凸形状を有する側と反対側が接するように、被着材に積層されて用いられてもよい。
一方、上記絵柄層を有する被着材を用いる場合、該絵柄層を有する被着材上に、上記透明性樹脂フィルムを積層することにより、本発明の化粧板を得ることができる。
なお、上記絵柄層としては、上述した絵柄層を好適に用いることができる。
上記被着材の材質は、例えば、木材単板、木材合板、パーチクルボード、MDF(中密度繊維板)等の木質板;石膏板、石膏スラグ板等の石膏系板;珪酸カルシウム板、石綿スレート板、軽量発泡コンクリート板、中空押出セメント板等のセメント板;パルプセメント板、石綿セメント板、木片セメント板等の繊維セメント板;陶器、磁器、土器、硝子、琺瑯等のセラミックス板;鉄板、亜鉛メッキ鋼板、ポリ塩化ビニルゾル塗布鋼板、アルミニウム板、銅板等の金属板;ポリオレフィン樹脂板、アクリル樹脂板、ABS板、ポリカーボネート板等の熱可塑性樹脂板;フェノール樹脂板、尿素樹脂板、不飽和ポリエステル樹脂板、ポリウレタン樹脂板、エポキシ樹脂板、メラミン樹脂板等の熱硬化型樹脂板;フェノール樹脂、尿素樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、メラミン樹脂、ジアリルフタレート樹脂等の樹脂を、硝子繊維不織布、布帛、紙、その他の各種繊維質基材に含浸硬化して複合化したいわゆるFRP板等が挙げられ、これらを単独で用いてもよく、これらの2種以上を積層した複合基板として用いてもよい。
なお、上記被着材の厚みは特に限定されない。
上記被着材への積層方法としては特に限定されるものではなく、例えば、上述したプライマー層を介して積層したり、接着剤を介して積層したりする手段等が挙げられる。
上記接着剤としては、上記被着材の種類等に応じて公知の接着剤から適宜選択すれば良い。例えば、ポリ酢酸ビニル、ウレタン、アクリル、ウレタンアクリル(共重合体も含む)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。
<化粧板の製造方法>
本発明の化粧板の製造方法としては、例えば、加熱溶融法や熱ラミネート法、そして水系接着剤や感熱接着剤、感圧接着剤の他、ホットメルト接着剤、上述した透明接着剤層を形成する接着剤等を用いて、上記基材、上記絵柄層、及び、上記透明性樹脂フィルムを積層させる方法等が挙げられる。
なかでも、上記化粧板の製造方法であって、上記透明性樹脂フィルムの上記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が好ましい。
このような本発明の化粧板を製造する方法もまた、本発明の一態様である。
上記透明性樹脂フィルムでは、上記絵柄層を積層される側の反対側面に有する凹凸形状を賦形する際に、エンボス加工等を施して凹凸形状を形成するが、エンボス加工を施した面側の凹凸形状に追従して、エンボス加工を施した面と反対側の面(上記絵柄層に積層される側の面)にも多少の凹凸形状が賦形されてしまう。このような場合には、上記透明性樹脂フィルムに形成された上記絵柄層が積層される側の凹凸形状に空気が入り込む、いわゆるエア噛みが発生し、意匠性が低下することがある。
本発明の化粧板の製造方法では、上記透明性樹脂フィルムの上記絵柄層を有する側の面に接着剤層を形成する工程を有するので、上記絵柄層を有する側の凹凸形状の凹部にも接着剤層を入り込ますことができ、上述したエア噛みの発生を防止し、意匠性の低下を抑制することができる。
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によってなんら限定されるものではない。
(実施例1)
透明ポリプロピレンフィルム(厚み60μm)を用意し、該透明ポリプロピレンフィルムの一方の面にシリカを添加したイソシアネートを硬化剤とする2液硬化型ウレタン樹脂(厚み1μm)を塗工し表面保護層用プライマー層を形成した。
上記透明ポリプロピレンフィルムのもう一方の面(表面保護層用プライマー層が塗工されていない側)に、透明ポリプロピレン系樹脂(厚み200μm)を押し出し熱ラミネート方式で積層した。その表面にコロナ処理を施した後、外部ヘイズ層となるイソシアネートを硬化剤とする2液硬化型ウレタン樹脂(厚み2μm)を塗工した。その表面保護層用プライマー層の塗工面に電子線硬化型樹脂であるウレタン(メタ)アクリレートを塗布量15μmとなるように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、5Mradの条件で電子線を照射し表面保護層を形成した。その後、その面がエンボス版と接触するよう、熱吸収式エンボス加工を行い、凹凸形状を賦形させ、透明性樹脂フィルムを製造した。
その後、ヘイズ測定機を用いて透明性樹脂フィルム全体のヘイズ値、裏面が濡れた状態でのヘイズを後述する方法で測定した。
その一方、HDF(厚み3mm)を用意し、該HDFの一方の面上にインクジェットプリンターにて厚みが2μmとなるように絵柄層を形成して基材を準備した。 
得られた透明性樹脂フィルムの凹凸形状を有する側と反対側面に、イソシアネートを硬化剤とする2液硬化型ポリエステル樹脂(厚み50μm)を塗布して接着剤層を形成し、得られた透明性樹脂フィルムの凹凸形状を有する側と反対側面と、上記基材の絵柄層側を備える面とを上記接着剤層を介して積層した。その後、10kg/mの圧力を掛け3日間、常温環境下で養生した。
(ヘイズ値測定方法)
測定装置として、DIRECT HAZE METER(東洋精機社製)を使用した。
シート全体のヘイズ値:透明性樹脂フィルムの凹凸形状を有する面側、具体的には実施例1では凹凸形状を賦型された表面保護層の側から光を当ててヘイズ値を測定した。
裏面が濡れた状態でのヘイズ値:透明性樹脂フィルムの外部ヘイズ層を有する面側に純水を滴下させ、PETフィルム(東レ社製ルミラーT60 50μm厚、ヘイズ値0.1%)を空気が噛まないようにして積層し、その状態で透明性樹脂フィルムの凹凸形状を有する面側、具体的には実施例1では凹凸形状を賦型された表面保護層の側から光を当ててヘイズ値を測定した。
外部ヘイズ層のヘイズ値:シート全体のヘイズ値から裏面が濡れた状態でのヘイズ値を引いた値として算出した。
(エア噛みの目視確認)
++・・・エア噛みが明らかに判断できる
+・・・エア噛みが斜光にて確認することで判断できる
-・・・エア噛みが判断できない
(密着時の意匠性)
+++・・・ラミネート後の意匠が非常にクリアに見える
++・・・ラミネート後の意匠が僅かに曇って見える
+・・・ラミネート後の意匠が非常に曇って見える
-・・・ラミネート後の意匠がほとんどみえない
(実施例2~4、参考例1)
表1に示したように外部ヘイズ層のヘイズ値の異なるサンプルを用いた以外は、実施例1と同様にして透明性樹脂フィルムを製造した。その後、実施例1と同様の評価を行った。
Figure JPOXMLDOC01-appb-T000001
実施例1~4で得られた透明性樹脂フィルムでは、エア噛みを容易に目視確認することができた。
一方で、参考例1で得られた透明性樹脂フィルムでは、エア噛みを目視確認することができなかった。
(実施例5)
ポリプロピレン系樹脂(厚み60μm)を用意し、その一方の面(絵柄層を有する基材に積層される側)に、プライマー剤を塗工し、外部ヘイズ層(厚み2μm、イソシアネートを硬化剤とする2液硬化型ウレタン樹脂)を形成した。上記ポリプロピレン系樹脂のもう一方の面に、ポリプロピレン系樹脂(厚み60μm)を押出し熱ラミネート方式により積層した。その直後に、温度を10℃にした金属ロールに0.5秒間接触させて、200℃/秒で冷却(急冷)し、外部ヘイズ層が形成された透明性樹脂層を得た。
次いで、透明性樹脂層の外部ヘイズ層を有する面と反対側の表面にコロナ処理を施した後、プライマー剤(厚み2μm)を塗工し、表面保護層用プライマー層を形成した。その表面に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、5Mradの条件で電子線を照射し表面保護層を形成した。
その後、表面保護層を有する側を、赤外線非接触方式のヒーターで加熱した後、熱圧によるエンボス加工を行い、凹凸形状を有する透明性樹脂フィルムを得た。
透明性樹脂フィルムの外部ヘイズ層を有する面に、2液硬化型ポリエステル(厚み50μm)を塗工して接着剤層を形成し、インクジェットプリンターで厚み2μmとなるように設けた絵柄層を有する基材(MDF(中密度繊維板)厚み3mm)上に積層し、化粧板を得た。
(実施例6)
外部ヘイズ層の厚みを1μmに変更したこと以外は、実施例5と同様にして化粧板を作製した。
(実施例7)
外部ヘイズ層の厚みを5μmに変更したこと以外は、実施例5と同様にして化粧板を作製した。
(参考例2)
外部ヘイズ層の厚みを0.5μmに変更したこと以外は、実施例5と同様にして化粧板を作製した。
(参考例3)
ポリプロピレン系樹脂(厚み60μm)を用意し、その一方の面に、プライマー剤(厚み2μm、イソシアネートを硬化剤とする2液硬化型ウレタン樹脂)を塗工し、外部ヘイズ層を形成した。上記ポリプロピレン系樹脂のもう一方の面に、ポリプロピレン系樹脂(厚み60μm)を押出し熱ラミネート方式により積層した。その直後に、50℃の金属ロールに0.5秒間接触させた後、25℃環境下にて放置し、更に50℃/秒で冷却(徐冷)して、外部ヘイズ層が形成された透明性樹脂層を得た。
上記以外は、実施例5と同様にして化粧板を作製した。
<ヘイズ値>
実施例5~7及び参考例2~3で得られた透明性樹脂フィルムの基材に積層される側と反対側の表面ヘイズを除いたヘイズ値(1)と、基材に積層される側の表面ヘイズと、基材に積層される側と反対側の表面ヘイズとを除いたヘイズ値(2)は、下記方法により測定した。
<ヘイズ値(1)>
透明性樹脂フィルム、純水、及び、PETフィルム(東レ社製ルミラーT60 100μm厚、ヘイズ値1.5%)が、この順に積層されたシートを作製した。
このとき、透明性樹脂フィルムの凹凸形状を有する側に、上記純水が積層されるようにした。
得られたシートについて、透明性樹脂フィルムの凹凸形状を有する側、より具体的には透明性樹脂フィルムの凹凸形状を有する側に積層されたPETフィルムの側から、DIRECT READING HAZE METER(東洋精機社製)を用い、ヘイズ値を測定し、上記PETフィルムのヘイズ値を除く、具体的にはPETフィルムのへイズ値1.5%を引くことにより、ヘイズ値(1)を得た。
<ヘイズ値(2)>
PETフィルム(東レ社製ルミラーT60 100μm厚、ヘイズ値1.5%)、純水、透明性樹脂フィルム、純水、及び、PETフィルム(東レ社製、ルミラーT60、100μm厚、ヘイズ値1.5%)が、この順に積層されたシートを作製した。
得られたシートについて、透明性樹脂フィルムの凹凸形状を有する側、より具体的には透明性樹脂フィルムの凹凸形状を有する側に積層されたPETフィルムの側から、DIRECT READING HAZE METER(東洋精機社製)を用い、ヘイズ値を測定し、上記PETフィルムのヘイズ値を除く、具体的には、PETフィルムのへイズ値それぞれ1.5%、合計で3%を引くことにより、ヘイズ値(2)を得た。
(凹凸形状の賦形性)
実施例5~7及び参考例2~3で得られた透明性樹脂フィルムについて、凹凸形状が形成された側(表面保護層を有する側)のグロス値(G)を測定した。
次いで、透明性樹脂フィルムを、100℃のグリセリン中に30秒間浸漬した後、冷水にて冷却し、再度凹凸形状が形成された側のグロス値(G)を測定した。
以下の評価基準により、凹凸形状の賦形性を評価した。(G)と(G)とが近い値であるほど、凹凸模様の消失が少ないことを意味する。
なお、グロス値の測定では、グロス計(村上色彩技術研究所社製 GMX-202(角度60°)を使用した。なお、この測定はJIS Z8741に準拠している。
++:(G)/(G)が80%以上である。
+:(G)/(G)が60%以上、80%未満である。
-:(G)/(G)が60%未満である。
(意匠性)
実施例5~7及び参考例2~3で得られた化粧板を目視にて観察し、以下の基準で評価した。
++:絵柄層に形成された印刷柄が、明瞭に見える。
+:絵柄層に形成された印刷柄が、僅かに変色(曇って)見える。
-:絵柄層に形成された印刷柄が、明瞭に見えない。
Figure JPOXMLDOC01-appb-T000002
実施例5~7で得られた透明性樹脂フィルムは、凹凸形状の賦形性に優れ、実施例で得られた化粧板は意匠性にも優れることが確認された。
一方、ヘイズ(1)が70%未満であった参考例2は凹凸形状の賦形性に劣り、ヘイズ値(2)が70%を超えていた参考例3では、意匠性に劣っていた。
本発明によれば、基材の絵柄層と透明性樹脂フィルムとの接着の可否を目視で確認できる透明性樹脂フィルムを提供できる。本発明の化粧板は、内装用の建材である建具や引き戸等の扉、床材、壁、天井、そして様々な加飾成型体等に好適に用いられる。
10 本発明の透明性樹脂フィルム
11 熱可塑性樹脂層
12 外部ヘイズ層
13 表面保護層用プライマー層
14 表面保護層
20 化粧板
23 接着剤層
24 絵柄層
25 基材

 

Claims (8)

  1. 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、
    前記透明性樹脂フィルムは、少なくとも、熱可塑性樹脂層と、前記絵柄層に積層される側に外部ヘイズ層とを有する
    ことを特徴とする透明性樹脂フィルム。
  2. 前記外部ヘイズ層のヘイズ値が4%以上、100%未満である請求項1記載の透明性樹脂フィルム。
  3. 前記外部ヘイズ層の熱可塑性樹脂層側と反対側に純水層を介してヘイズ値が0.1%以下のポリエチレンテレフタレートフィルムを貼り付け、前記熱可塑性樹脂層側から測定した裏面が濡れた状態でのヘイズ値が90%以下である請求項1又は2記載の透明性樹脂フィルム。
  4. 前記外部ヘイズ層の厚みが0.5μm以上、20μm以下である請求項1、2又は3記載の透明性樹脂フィルム。
  5. 前記透明性樹脂フィルムは、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、
    前記絵柄層に積層される側と反対側の表面ヘイズを除いたヘイズ値であるヘイズ値(1)が、70%以上であり、
    前記絵柄層に積層される側の表面ヘイズと、前記絵柄層に積層される側と反対側の表面ヘイズとを除いたヘイズ値であるヘイズ値(2)が、70%以下である
    請求項1記載の透明性樹脂フィルム。
  6. 前記熱可塑性樹脂層の前記絵柄層に積層される側と反対側に、表面保護層を有する請求項1、2、3、4又は5に記載の透明性樹脂フィルム。
  7. 厚み方向において順に、基材と、絵柄層と、請求項1、2、3、4、5又は6記載の透明性樹脂フィルムとを備えることを特徴とする化粧板。
  8. 請求項7記載の化粧板の製造方法であって、
    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。

     
PCT/JP2019/038611 2018-10-12 2019-09-30 透明性樹脂フィルム、化粧板及び化粧板の製造方法 WO2020075565A1 (ja)

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