阅读说明：本技术 装饰板、透明性树脂膜和装饰板的制造方法 (Decorative sheet, transparent resin film, and method for producing decorative sheet ) 是由 古田哲 藤井亮 中岛智美 根津义昭 茅原利成 住田阳亮 于 2019-09-30 设计创作，主要内容包括：本发明提供一种装饰板、透明性树脂膜和装饰板的制造方法,即使在透明性树脂膜的最表面形成有凹凸形状,也能够在该透明性树脂膜的凹凸形状的凹部具有优异的耐候性。本发明的装饰板为在厚度方向依次叠层有基材、图案层和透明性树脂膜的装饰板,该装饰板的特征在于,上述透明性树脂膜至少具有热塑性树脂层,并且在叠层上述图案层的一侧的相反侧具有凹凸形状,在上述图案层与上述热塑性树脂层之间,具有至少1层含有紫外线吸收剂的层。(The invention provides a decorative sheet, a transparent resin film and a method for manufacturing the decorative sheet, wherein even if the concave-convex shape is formed on the outermost surface of the transparent resin film, the concave-convex shape of the transparent resin film has excellent weather resistance. The decorative sheet of the present invention is a decorative sheet comprising a substrate, a pattern layer and a transparent resin film laminated in this order in the thickness direction, wherein the transparent resin film comprises at least a thermoplastic resin layer, and has a concavo-convex shape on the side opposite to the side on which the pattern layer is laminated, and at least 1 layer containing an ultraviolet absorber is provided between the pattern layer and the thermoplastic resin layer.)

1. A decorative sheet comprising a base material, a pattern layer and a transparent resin film laminated in this order in the thickness direction, characterized in that:

the transparent resin film has at least a thermoplastic resin layer and has a concavo-convex shape on the opposite side of the side where the pattern layer is laminated,

between the pattern layer and the thermoplastic resin layer, at least 1 layer containing an ultraviolet absorber is provided.

2. The trim panel of claim 1 wherein:

the thickness of the concave-convex shaped concave part of the transparent resin film is more than 80 μm.

3. The decorative panel of claim 1 or 2, wherein:

the transparent resin film has a concavo-convex shape on the side where the pattern layer is laminated.

4. The trim panel of claim 3 wherein:

the transparent resin film has an irregular shape on the side where the pattern layer is laminated, and Rzmax defined in JIS B0601(2001) is 80 [ mu ] m or less.

5. The trim panel of claim 1, 2, 3 or 4 wherein:

an adhesive layer is provided between the pattern layer and the transparent resin film.

6. The trim panel of claim 5 wherein:

the adhesive layer has a thickness of 10 [ mu ] m or more and is larger than Rzmax defined in JIS B0601(2001) in the uneven shape of the transparent resin film on the side where the pattern layer is laminated.

7. The decorative panel of claim 5 or 6, wherein:

the adhesive layer is a layer containing the ultraviolet absorber.

8. The trim panel of claim 7 wherein:

the adhesive layer contains an ultraviolet absorber in an amount of 0.5 to 2 mass%.

9. The decorative panel of claim 7 or 8, wherein:

the ultraviolet absorber contained in the adhesive layer is a triazine-based ultraviolet absorber.

10. The trim panel of claim 1, 2, 3, 4, 5, 6, 7, 8, or 9 wherein:

the transparent resin film has an adhesion primer layer on the side of the thermoplastic resin layer on which the pattern layer is laminated.

11. The trim panel of claim 10 wherein:

the adhesive primer layer is a layer containing the ultraviolet absorber.

12. The trim panel of claim 11 wherein:

the ultraviolet absorber contained in the adhesive primer layer is a triazine-based ultraviolet absorber.

13. The decorative panel of claim 10, 11 or 12, wherein:

the thickness of the adhesive primer layer is 0.5 to 10 [ mu ] m.

14. A transparent resin film characterized by:

for protecting a patterned layer laminated to one side of a substrate and for use in a decorative sheet according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13.

15. A method for manufacturing a decorative panel according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, comprising:

forming an adhesive layer on one surface of the transparent resin film on which the pattern layer is laminated; and

and a step of bonding the transparent resin film and the pattern layer via the adhesive layer.

Technical Field

The invention relates to a decorative sheet, a transparent resin film, and a method for manufacturing the decorative sheet.

Background

In recent years, due to the spread of the inkjet printing method using an inkjet printer, it has become possible to apply a pattern layer to a decorative sheet used for building materials, decorative molded articles, and the like, which is capable of coping with production of various products, small lot, and complicated printing of patterns (characters, numbers, figures, and the like).

Moreover, the inkjet printing method has the following advantages: the printed substrate is not limited to a film, and printing can be performed on a flat plate or a substrate having irregularities and a curved surface.

However, since the pattern layer printed by the inkjet printing method is the outermost surface of the substrate, the surface properties such as scratch resistance, stain resistance, and weather resistance are insufficient, and a transparent resin film is required to protect the pattern layer.

As such a transparent resin film, for example, patent document 1 discloses a laminated film in which a protective layer is provided on one surface of a 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.

However, in the conventional decorative sheet having a transparent resin film, the design is improved by providing the transparent resin film with the uneven shape, but the uneven weather resistance is caused by the difference in thickness of the transparent resin film due to the uneven shape, and particularly, the weather resistance is poor in the film portion, and there is still room for improvement. In particular, various inks are used for pattern layers printed by an inkjet printing method, and the tendency thereof is remarkable.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2005-120255

Disclosure of Invention

Problems to be solved by the invention

The invention aims to provide a decorative sheet, a transparent resin film and a method for manufacturing the decorative sheet, wherein even if the surface of the transparent resin film is provided with concave-convex shapes, the concave-convex shapes of the transparent resin film can have excellent weather resistance.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that a decorative sheet having excellent weather resistance even when an uneven shape is formed on the surface can be obtained by laminating a base material, a pattern layer, and a transparent resin film in this order in the thickness direction, the transparent resin film having at least a thermoplastic resin layer, the uneven shape being formed on the opposite side to the side on which the pattern layer is laminated, and at least 1 layer containing an ultraviolet absorber being provided between the pattern layer and the thermoplastic resin layer, and have completed the present invention.

The decorative sheet of the present invention is a decorative sheet in which a base material, a pattern layer and a transparent resin film are sequentially laminated in a thickness direction, the decorative sheet characterized in that: the transparent resin film has at least a thermoplastic resin layer, and has a concavo-convex shape on the opposite side of the side on which the pattern layer is laminated, and at least 1 layer containing an ultraviolet absorber is provided between the pattern layer and the thermoplastic resin layer.

The decorative sheet of the present invention is preferably such that the thickness of the recessed portions of the uneven shape of the transparent resin film is 80 μm or more.

Preferably, the transparent resin film has a concave-convex shape on the side where the pattern layer is stacked.

Preferably, Rzmax of the uneven shape of the transparent resin film on the side where the pattern layer is laminated, which is defined in JIS B0601(2001), is 80 μm or less.

Preferably, an adhesive layer is provided between the pattern layer and the transparent resin film.

Preferably, the adhesive layer has a thickness of 10 μm or more and is larger than Rzmax defined in JIS B0601(2001) in the uneven shape of the transparent resin film on the side where the pattern layer is laminated.

Preferably, the adhesive layer is a layer containing the ultraviolet absorber.

Preferably, the adhesive layer contains 0.5 mass% to 2 mass% of an ultraviolet absorber.

Preferably, the ultraviolet absorber contained in the adhesive layer is a triazine-based ultraviolet absorber.

Preferably, the transparent resin film has an adhesion primer layer on the side of the thermoplastic resin layer on which the pattern layer is laminated.

Preferably, the adhesive primer layer is a layer containing the ultraviolet absorber.

Preferably, the ultraviolet absorber contained in the adhesive primer layer is a triazine-based ultraviolet absorber.

The thickness of the adhesive primer layer is preferably 0.5 μm or more and 10 μm or less.

The transparent resin film of the present invention is preferably used for protecting a pattern layer laminated on one side of a substrate.

Preferably, the method for manufacturing a decorative sheet of the present invention includes: forming an adhesive layer on one surface of the transparent resin film on which the pattern layer is laminated; and a step of bonding the transparent resin film and the pattern layer via the adhesive layer.

Effects of the invention

The decorative sheet of the present invention has excellent weather resistance even when the surface of the transparent resin film has irregularities.

In addition, the transparent resin film of the present invention can impart excellent weather resistance to the decorative sheet.

Drawings

Fig. 1 is a sectional view schematically showing a preferred example of the decorative sheet of the present invention.

Fig. 2 is a sectional view schematically showing a preferred example of the transparent resin film constituting the decorative sheet of the present invention.

Fig. 3 is a sectional view schematically showing a preferred example of the transparent resin film constituting the decorative sheet of the present invention.

Detailed Description

The decorative sheet of the present invention will be explained first.

The decorative sheet of the present invention is a decorative sheet in which a base material, a pattern layer and a transparent resin film are sequentially laminated in a thickness direction, the decorative sheet characterized in that: the transparent resin film has at least a thermoplastic resin layer, and has a concavo-convex shape on the opposite side of the side on which the pattern layer is laminated, and at least 1 layer containing an ultraviolet absorber is provided between the pattern layer and the thermoplastic resin layer.

A preferred example of the decorative sheet of the present invention will be described with reference to fig. 1.

Fig. 1 is a sectional view schematically showing a preferred example of the decorative sheet of the present invention.

As shown in fig. 1, a decorative sheet 10 of the present invention is formed by sequentially laminating a base material 11, a pattern layer 12 and a transparent resin film 20 in a thickness direction, and has a concavo-convex shape on the opposite side of the transparent resin film 20 from the side where the pattern layer 12 is laminated.

As shown in fig. 1, an adhesive layer 13 is preferably provided between the pattern layer 12 and the transparent resin film 20.

Hereinafter, each structure of the decorative sheet of the present invention will be described.

In the following description, the upper limit of the lower limit of the numerical range represented by "-" is "at least" and (not less than) "in the following description (for example, when α to β are described, α to β are represented).

[ base Material ]

In the decorative sheet of the present invention, a base material, a pattern layer, and a transparent resin film are laminated in this order in the thickness direction.

The substrate is not particularly limited, and may be appropriately determined according to the use of the decorative sheet of the present invention.

The material constituting the base material is not particularly limited, and examples thereof include known materials such as resin materials, wood materials, and metal materials. Among them, as a material constituting the base material, a resin material or a wood material having rigidity and light weight is preferable. Further, a composite material thereof is also possible.

The resin material preferably contains, for example, a thermoplastic resin.

The thermoplastic resin is preferably a monomer or a copolymer of a polyvinyl resin such as a polyvinyl chloride resin, a polyvinyl acetate resin, or a polyvinyl alcohol resin, a polyolefin resin such as polyethylene, polypropylene, polystyrene, an ethylene-vinyl acetate copolymer resin (EVA), or an ethylene- (meth) acrylic resin, a polyester resin such as a polyethylene terephthalate resin (PET resin), an acrylate resin, a polycarbonate resin, a polyurethane resin, an acrylonitrile-butadiene-styrene copolymer resin (ABS resin), or an acrylonitrile-styrene copolymer resin, or a mixed resin thereof. Among them, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins, polyvinyl chloride resins, ionomers, and the like are preferable. Further, the resin material may be foamed.

Examples of the wood material include various materials such as fir, hinoki, beech, pine, eucalyptus, teak, and willow white (melapi), and the core material may be any of sliced veneer, wood plywood (including LVL), particle board, Medium Density Fiberboard (MDF), High Density Fiberboard (HDF), and laminated wood made of these materials, or a laminated material obtained by laminating these materials appropriately.

Examples of the metal material include iron.

The base material may contain an inorganic compound. By containing the inorganic compound, the linear expansion coefficient of the base material can be reduced, and as a result, the water resistance of the transparent resin film described later can be improved.

In the case where the base material includes a base material made of a plurality of resins, the types of resins forming the base material made of the plurality of resins may be the same or different, and the thicknesses of the base materials made of the plurality of resins may be the same or different.

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

The thickness of the substrate is not particularly limited, and is, for example, preferably 0.01mm or more, and more preferably 0.1mm or more and 50mm or less.

The substrate includes a substantially plate-like substrate other than a flat plate, and also includes a substrate having irregularities or curved surfaces.

[ Pattern layer ]

In the decorative sheet of the present invention, a pattern layer is laminated on one surface side of the base material.

The pattern layer is a layer for providing a decorative property to the decorative sheet of the present invention, and may be, for example, a masking layer (a full-coat printed layer) to which a coloring is uniformly applied, a pattern layer formed by printing various patterns using an ink or a printer, or a layer in which a masking layer and a pattern layer are combined (hereinafter, referred to as a pattern layer).

By providing the shielding layer, when the base material is colored or has color unevenness, the color of the surface can be adjusted by providing an intentional color.

Further, by providing the pattern layer, it is possible to impart a stone pattern such as a wood grain pattern or a marble pattern (for example, a travertine marble pattern) imitating a rock surface, a cloth pattern such as a cloth pattern or a cloth-like pattern, a tile pattern, a brick pile pattern, or a wood block or a cloth block obtained by combining these patterns to the decorative sheet. These patterns can be formed by multicolor printing using ordinary yellow, red, blue, and black printing colors, or by multicolor printing using specific colors by preparing plates of the respective colors constituting the patterns.

As the ink composition used for the pattern layer, a composition in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed with a binder resin can be used. The binder resin is not particularly limited, and examples thereof include a urethane resin, an acrylate resin, a urethane-acrylate copolymer resin, a vinyl chloride/vinyl acetate/acrylate copolymer resin, an acrylate resin, a polyester resin, and a nitrocellulose resin. The binder resin may be selected from any of them and used alone in 1 kind or in a mixture of 2 or more kinds.

Further, preferable examples of the colorant include carbon black (ink), inorganic pigments such as iron black, titanium white, antimony white, chrome yellow, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, and pearl luster pigments (pearl pigments) composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate.

The thickness of the pattern layer is not particularly limited, and is, for example, preferably 0.1 μm or more, and more preferably 0.5 μm or more and 600 μm or less. If the thickness of the pattern layer is within the above range, the decorative sheet of the present invention can be provided with an excellent design and can also be provided with a masking property.

When the base material itself has design properties in advance, such as plywood, the base material may not be provided with a pattern layer.

[ layer containing ultraviolet absorber ]

The decorative sheet of the present invention has at least 1 layer containing an ultraviolet absorber between the pattern layer and a thermoplastic resin layer of a transparent resin film described later.

The layer containing an ultraviolet absorber may be an adhesive primer layer provided in a transparent resin film described later, may be an adhesive layer described later, or may be both of the layers containing an ultraviolet absorber.

[ transparent resin film ]

In the decorative sheet of the present invention, a transparent resin film is laminated on the side of the pattern layer opposite to the base material.

The transparent resin film has at least a thermoplastic resin layer and has a concavo-convex shape on the side opposite to the side on which the pattern layer is laminated.

[ thermoplastic resin layer ]

The thermoplastic resin layer is a layer having a function of protecting a pattern layer laminated on one surface of a substrate, which will be described later. The thermoplastic resin layer may be translucent or colored as long as it is transparent and in a range where the pattern layer can be seen.

Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polybutylene, polymethylpentene, and olefin-based thermoplastic elastomers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer resins, terephthalic acid-ethylene glycol-1, 4-cyclohexanedimethanol copolymer resins, polyester resins such as polyester-based thermoplastic elastomers, acrylate resins such as polymethyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer resins, and methyl (meth) acrylate-styrene copolymer resins, polycarbonate resins, polyvinyl chloride, polystyrene, and ionomers. Among them, polypropylene is preferred in view of high tensile strength, excellent chemical resistance and excellent production process.

In the present specification, the term (meth) acrylate refers to acrylate or methacrylate.

The thermoplastic resin layer may be unstretched, or may be uniaxially or biaxially stretched as necessary.

The thickness of the thermoplastic resin layer is not particularly limited, but is preferably 20 μm at the lower limit, more preferably less than 500 μm at the upper limit, even more preferably 60 μm at the lower limit, and even more preferably 420 μm at the upper limit. When the thickness of the thermoplastic resin layer is less than 20 μm, the tensile strength may become insufficient to protect the surface of the pattern layer, and when the thickness is 500 μm or more, the light transmittance of the transparent resin layer may decrease to lower the visibility of the pattern layer.

The thermoplastic resin layer may be a laminate of 1 layer or 2 or more layers.

In the case where the thermoplastic resin layer is composed of a plurality of layers, the types of resins to be formed may be the same or different, and the thicknesses of the substrates composed of a plurality of types of resins may be the same or different.

The method of laminating the thermoplastic resin layers to 2 or more layers is not limited as long as it is a general method, and a dry lamination method, an extrusion thermal lamination method, and the like can be mentioned.

The thermoplastic resin layer may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, plasma discharge treatment, Ultraviolet (UV) treatment, flame treatment, or the like, within a range not departing from the gist of the present invention.

[ primer for adhesion ]

In the transparent resin film, it is preferable that the thermoplastic resin layer has an adhesion primer layer on a side where the pattern layer is laminated.

By providing the adhesion primer layer, the adhesion between the transparent resin film and the pattern layer can be further enhanced.

Preferably, the adhesive primer layer contains a binder resin.

Examples of the binder resin include urethane resin, acrylate-urethane copolymer resin, cellulose resin, polyester resin, and vinyl chloride-vinyl acetate copolymer resin. When the urethane acrylate oligomer is blended in the ionizing radiation curable resin composition of the surface protective layer described later, it is preferable to contain a urethane resin from the viewpoint of adhesion to the pattern layer and efficiency in production.

The thickness of the adhesive primer layer is preferably 0.5 μm to 10 μm. When the thickness is 0.5 μm or more, the adhesion to the pattern layer can be satisfactorily ensured, and when the thickness is 10 μm or less, the transparent resin film can be made not to be excessively thick, sufficient transparency can be obtained, and the design of the decorative sheet can be satisfactorily ensured. In addition, blocking during film formation can also be suppressed. Note that blocking means: in the case of forming a transparent resin film, after applying an adhesive primer or the like, the film is wound into a roll, and then the film is hard to separate from each other when the film is unwound.

The adhesive primer layer may contain inorganic fine particles such as silica.

The adhesive primer layer is preferably a layer containing the ultraviolet absorber.

By providing the adhesive primer layer with the layer containing the ultraviolet absorber, the decorative sheet of the present invention can be favorably provided with weather resistance.

As the ultraviolet absorber, for example, an organic or inorganic ultraviolet absorber can be used. Among them, organic ultraviolet absorbers having excellent transparency are preferably used.

Examples of the organic ultraviolet absorber include benzotriazole ultraviolet absorbers such as 2 '-hydroxyphenyl-5-chlorobenzotriazole (e.g., 2- (2' -hydroxy-3 ', 5' -di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-i-butyl-5' -propylphenyl) -5-chlorobenzotriazole (e.g., 2 '-hydroxyphenyl-5-chlorobenzotriazole), 2- (2' -hydroxy-3 ', 5' -di-t-butylphenyl) benzotriazole, and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (e.g., 2 '-hydroxyphenylbenzotriazole ultraviolet absorbers), benzotriazole (e.g., 2' -hydroxybenzotriazole), Benzophenone-based ultraviolet absorbers such as 2,2 '-dihydroxybenzophenone-based ultraviolet absorbers including 2, 2' -dihydroxy-4-methoxybenzophenone, 2 '-dihydroxy-4, 4' -dimethoxybenzophenone and 2,2 '-dihydroxy-4, 4' -tetrahydroxybenzophenone, benzophenone-based ultraviolet absorbers including 2-hydroxybenzophenone-based ultraviolet absorbers including 2-hydroxy-4-methoxybenzophenone and 2, 4-dihydroxybenzophenone, and salicylate-based ultraviolet absorbers such as phenyl salicylate and 4-tert-butyl-phenyl salicylate.

In particular, triazine-based ultraviolet absorbers are preferred from the viewpoint of imparting weather resistance, design properties, suppression of bleeding, and the like.

Examples of the triazine-based ultraviolet absorber include 2, 4-bis (2, 4-dimethylphenyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4 '- (1,3, 5-triazine-2, 4, 6-triyltrimethyleneamino) tribenzoic acid tris (2-ethylhexyl), 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, N' -tris (m-tolyl) -1, 3, 5-triazine-2, 4, 6-triamine, 2,4, 6-tris (4-butoxy-2-hydroxyphenyl) -1, 3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ 2- (2-ethylhexanoyloxy) ethoxy ] phenol, and the like.

In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton can be used. Alternatively, an inorganic ultraviolet absorber may be added to the composition without requiring high transparency. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, iron oxide, etc. having a particle size of 0.2 μm or less can be used.

The content of the ultraviolet absorber can be appropriately determined in accordance with the ultraviolet absorbing ability of the ultraviolet absorber to be used.

When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, the adhesion primer layer is preferably at least 1 mass% and at most 10 mass%.

When the content of the adhesion primer layer is less than 1% by mass, sufficient weather resistance may not be imparted, and when the content of the adhesion primer layer exceeds 10% by mass, the transparency of the film may be impaired to lower the design of the decorative sheet, or the adhesiveness to the pattern layer or the like may not be sufficiently obtained to lower the suitability for processing of the transparent resin film.

The content of the ultraviolet absorber is more preferably 2 mass% or more and 7 mass% or less.

[ surface protective layer ]

The transparent resin film preferably has a surface protective layer on the opposite side of the thermoplastic resin layer from the side on which the pattern layer is laminated.

By providing the surface protection layer, the durability (scratch resistance, stain resistance, weather resistance, etc.) of the transparent resin film can be improved, the surface of the pattern layer can be protected more effectively, and the reduction in design properties due to the scratch of the transparent resin film itself can be prevented more effectively.

The surface protection layer may have a single layer structure, may have a multilayer structure made of the same or different materials, or may be formed by appropriately mixing the following materials.

The surface protective layer is not particularly limited, and examples thereof include a protective layer composed of a crosslinked cured product of a two-pack curable resin or an ionizing radiation curable resin composition, and the crosslinked cured product is preferably transparent, but may be translucent or colored as long as it is transparent and is in a range where a pattern layer described later can be recognized.

The two-part curable resin may be a binder resin of the adhesive primer layer.

As the ionizing radiation curable resin, for example, an oligomer having a radical polymerizable unsaturated bond or a cation polymerizable functional group in a molecule (hereinafter, also referred to as a prepolymer, a macromer, and the like) and/or a monomer having a radical polymerizable unsaturated bond or a cation polymerizable functional group in a molecule are preferably used. Here, the ionizing radiation refers to electromagnetic waves or charged particles having energy capable of polymerizing or crosslinking molecules, and generally refers to Electron Beams (EB) or ultraviolet rays (UV).

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

As the oligomer having a radical polymerizable unsaturated group in the molecule, for example, an oligomer such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, or triazine (meth) acrylate can be preferably used, and a urethane (meth) acrylate oligomer is more preferably used. As the molecular weight, about 250 to 10 ten thousand oligomers are usually used.

The monomer having a radical polymerizable unsaturated group in the molecule is preferably, for example, a polyfunctional monomer, and more preferably a polyfunctional (meth) acrylate.

Examples of the polyfunctional (meth) acrylate include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, bisphenol a ethylene oxide-modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate { 5-functional (meth) acrylate }, dipentaerythritol hexa (meth) acrylate { 6-functional (meth) acrylate }, and the like. Here, the polyfunctional monomer means a monomer having a plurality of radical polymerizable unsaturated groups.

In the present invention, the ionizing radiation curable resin composition more preferably 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, it is particularly preferable that the urethane acrylate oligomer/polyfunctional monomer (mass ratio) is 6/4 to 9/1. When the mass ratio is within the range, a composition having more excellent scratch resistance can be obtained.

If necessary, a monofunctional monomer may be used as appropriate in addition to the ionizing radiation curable resin component described above within a range not departing from the object of the present invention.

Examples of the monofunctional monomer include methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

When the ionizing radiation curable resin composition is crosslinked by ultraviolet rays, a photopolymerization initiator is preferably added to the ionizing radiation curable resin composition.

When the ionizing radiation curable resin composition is a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used alone or in combination as the photopolymerization initiator.

In the case of a resin system in which the ionizing radiation curable resin composition has a cationically polymerizable unsaturated group, the photopolymerization initiator may be an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, or the like, used alone or as a mixture. The amount of the photopolymerization initiator added is about 0.1 to 10 parts by mass per 100 parts by mass of the ionizing radiation curable resin component.

In addition, various additives may be added to the ionizing radiation curable resin composition as needed. Examples of the additives include thermoplastic resins such as polyurethane resins, polyvinyl acetal resins, polyester resins, polyolefin resins, styrene resins, polyamide resins, polycarbonate resins, acetal resins, vinyl chloride-vinyl acetate copolymer resins, vinyl acetate resins, acrylate resins, and cellulose resins, lubricants such as silicone resins, waxes, and fluororesins, ultraviolet absorbers such as benzotriazole, benzophenone, and triazine, light stabilizers such as hindered amine radical scavengers, and colorants such as dyes and pigments.

As the electron beam source of the ionizing radiation, various electron beam accelerators such as a kocroft-watton type, a van der graaff type, a resonance transformer type, an insulating core transformer type, a linear type, a high-frequency high-voltage accelerator type, and a high-frequency type can be used, and an electron beam source irradiating electrons having an energy of 70 to 1000keV can be used. The dose of the electron beam is preferably, for example, about 1 to 10 Mrad.

As the source of the ionizing radiation, a light source such as an ultra-high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, or a metal halide lamp can be used, and the wavelength of the ultraviolet ray is usually mainly in the wavelength range of 190 to 380 nm.

The thickness of the surface protective layer is not particularly limited, but is preferably 0.1 μm at the lower limit and 50 μm at the upper limit, more preferably 1 μm at the lower limit and 30 μm at the upper limit. When the thickness of the surface protective layer is less than 0.1 μm, it may be difficult to impart sufficient durability (scratch resistance, stain resistance, weather resistance, etc.), and when it exceeds 50 μm, the light transmittance of the transparent resin film of the present invention may be reduced, and the visibility of the pattern layer may be reduced.

Preferably, an undercoat layer for surface protection layer is provided between the surface protection layer and the thermoplastic resin layer.

By providing the primer layer for a surface protection layer, the adhesion between the surface protection layer and the thermoplastic resin layer can be further enhanced.

The primer layer for surface protection layer preferably contains the ultraviolet absorber. When the primer layer for a surface protective layer contains the ultraviolet absorber, the decorative sheet of the present invention can be more favorably provided with weather resistance.

As the primer layer for the surface protective layer, the same primer as the primer layer for adhesion can be preferably used.

[ concave-convex shape ]

The transparent resin film has a concavo-convex shape on the side opposite to the side on which the pattern layer is laminated.

The depth of the uneven shape on the side opposite to the side where the pattern layers are laminated is not particularly limited, but the center line average roughness Ra, which is defined by, for example, JIS B0601 (1982), is preferably adjusted to be in the range of 1 μm to 30 μm.

The transparent resin film may have a concave-convex shape on the side where the pattern layer is laminated.

When the transparent resin film has a convex shape in which a concave pattern layer is laminated on the side where the pattern layer is laminated, Rzmax defined in JIS B0601(2001) of the convex-concave shape is preferably 80 μm or less.

When Rzmax defined in JIS B0601(2001), which is an uneven shape on the side where the pattern layer is laminated, exceeds 80 μm, air bubbles are likely to enter between the pattern layer and the transparent resin film, and the design of the decorative sheet of the present invention may be deteriorated.

Rzmax defined in JIS B0601(2001) in the uneven shape on the side where the pattern layer is laminated is more preferably 60 μm or less.

In the present specification, Rzmax can be obtained by measurement under the following conditions using a surface roughness measuring instrument ("SURFCOM-FLEX-50A", manufactured by tokyo koku corporation).

(measurement conditions)

The number of times of measurement: n-5 (arbitrary 5 dots)

Calculating a standard: JIS' 01

The measurement types are as follows: roughness measurement

Evaluation length: 12.5mm

Cutoff value: 2.5mm

Measuring speed: 0.60mm/s

Filter type: gauss type

Shape removal: straight line

λ s value: 8.0 μm

When the uneven shape has directionality, the flow direction and the direction perpendicular thereto are measured, and the larger value of the two is taken as Rzmax.

The method for forming the above-mentioned uneven shape is not particularly limited, and examples thereof include embossing with heat, and a method of transferring an uneven shape to a shaped sheet.

As the embossing using heat, for example, a method of embossing using a known single-sheet type or rotary type embossing machine can be mentioned.

Examples of the embossed pattern include sand grain, hairline grain, pearskin grain, woodgrain duct groove, stone plate surface unevenness, cloth surface texture, and striae.

The temperature at which the embossing is performed is not particularly limited, but is preferably a temperature at which the indentation pattern does not disappear during the heat press-molding, that is, a temperature at which the embossing back is small.

In the case where the pattern layer is laminated on one side having an uneven shape, the uneven shape may be formed on both sides of the transparent resin film by the above-described method, or the uneven shape may be formed on one side of the transparent resin film by the above-described method so as to follow the uneven shape formed on the one side and form the uneven shape on the other side.

The thickness of the transparent resin film is not particularly limited, but the thickness of the concave portions of the uneven shape is preferably 80 μm or more. If the thickness of the recessed portions of the uneven shape of the transparent resin film is less than 80 μm, the decorative sheet of the present invention may not be sufficiently provided with durability (abrasion resistance and scratch resistance).

Here, the above-described "concave and convex shaped recess" will be described.

Fig. 2 and 3 are sectional views schematically showing a preferred example of the transparent resin film constituting the decorative sheet of the present invention.

In the transparent resin film 20 shown in fig. 2 and 3, an adhesion primer layer 21, a thermoplastic resin layer 22, a surface protection layer primer layer 23, and a surface protection layer 24 are laminated in this order in the thickness direction.

The "concave portion having a concave-convex shape" refers to a portion having the thinnest thickness of the transparent resin film and including the deepest concave portion having a concave-convex shape of the surface protection layer 24, and can be confirmed by observing the cross section of the transparent resin film 20 with a microscope.

In fig. 2, the length from the surface having the surface protection layer 24 to the opposite surface is the total thickness of the transparent resin film 20, and the length from the bottom of the deepest recess on the surface protection layer 24 side to the surface of the adhesion primer layer 21 is the "thickness of the recess having the uneven shape".

When the surface protection layer 24 has an uneven shape, the surface opposite to the uneven shape has a protrusion corresponding to the deepest recess of the uneven shape on the surface protection layer 24 side of the transparent resin layer 20, as shown in fig. 3, but the length from the bottom of the deepest recess of the uneven shape on the surface protection layer 24 side of the transparent resin layer 20 to the surface opposite to the surface having such a protrusion is "the thickness of the recess of the uneven shape".

The lower limit of the total thickness of the transparent resin film is preferably 100 μm, and the upper limit thereof is preferably 500 μm, more preferably 140 μm, and still more preferably 460 μm.

The upper limit of the thickness of the concave portions in the uneven shape of the transparent resin film is not particularly limited, but is preferably 500 μm, for example.

The transparent resin film is preferably used for protecting the pattern layer laminated on one side of the substrate.

Such a transparent resin film for protecting the pattern layer laminated on one side of the substrate is also an embodiment of the present invention.

[ adhesive layer ]

The decorative sheet of the present invention preferably has an adhesive layer between the pattern layer and a transparent resin film described later.

By having the adhesive layer, the adhesion between the pattern layer and the transparent resin film described later can be further strengthened.

The adhesive layer preferably contains a binder resin.

Examples of the binder resin include urethane resin, acrylate-urethane copolymer resin, cellulose resin, polyester resin, and vinyl chloride-vinyl acetate copolymer resin. When the urethane acrylate oligomer is blended in the ionizing radiation curable resin composition of the surface protective layer described later, a urethane resin is preferable from the viewpoint of adhesion between the pattern layer and the transparent resin film described later and efficiency in production.

The thickness of the adhesive layer is not particularly limited, but is preferably 10 μm or more, and when the side of the transparent resin film on which the pattern layer is laminated has an uneven shape, the thickness is larger than Rzmax defined in JIS B0601(2001) of the uneven shape.

When the thickness of the adhesive layer is 10 μm or more and is larger than Rzmax defined in JIS B0601(2001), which is an irregular shape of a side of the pattern layer to be laminated of a transparent resin film to be described later, adhesion between the pattern layer and the transparent resin film to be described later can be satisfactorily ensured.

On the other hand, when the thickness of the adhesive layer is less than 10 μm, adhesion between the pattern layer and the transparent resin film described later may not be sufficiently provided, and when Rzmax defined in JIS B0601(2001) having a smaller thickness than the uneven shape of the side of the transparent resin film on which the pattern layer is laminated is provided, air bubbles may enter between the pattern layer and the transparent resin film described later, which may deteriorate design properties.

The adhesive layer may contain inorganic fine particles such as silica.

The method of adhering the adhesive layer is not particularly limited, but can be obtained by, for example, a heat fusion method or a heat lamination method, and further, by laminating the adhesive layer using a hot melt adhesive or the like in addition to an aqueous adhesive, a heat sensitive adhesive or a pressure sensitive adhesive.

The adhesive layer is preferably a layer containing the ultraviolet absorber.

By providing the adhesive layer as the layer containing the ultraviolet absorber, excellent weather resistance can be favorably imparted to the decorative sheet of the present invention.

As the ultraviolet absorber, for example, an organic or inorganic ultraviolet absorber can be used. Among them, organic ultraviolet absorbers having excellent transparency are preferably used.

Examples of the organic ultraviolet absorber include benzotriazole ultraviolet absorbers such as 2 '-hydroxyphenyl-5-chlorobenzotriazole (e.g., 2- (2' -hydroxy-3 ', 5' -di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-i-butyl-5' -propylphenyl) -5-chlorobenzotriazole (e.g., 2 '-hydroxyphenyl-5-chlorobenzotriazole), 2- (2' -hydroxy-3 ', 5' -di-t-butylphenyl) benzotriazole, and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole (e.g., 2 '-hydroxyphenylbenzotriazole ultraviolet absorbers), benzotriazole (e.g., 2' -hydroxybenzotriazole), Benzophenone-based ultraviolet absorbers such as 2,2 '-dihydroxybenzophenone-based ultraviolet absorbers including 2, 2' -dihydroxy-4-methoxybenzophenone, 2 '-dihydroxy-4, 4' -dimethoxybenzophenone and 2,2 '-dihydroxy-4, 4' -tetrahydroxybenzophenone, benzophenone-based ultraviolet absorbers including 2-hydroxybenzophenone-based ultraviolet absorbers including 2-hydroxy-4-methoxybenzophenone and 2, 4-dihydroxybenzophenone, and salicylate-based ultraviolet absorbers such as phenyl salicylate and 4-tert-butyl-phenyl salicylate.

In particular, triazine-based ultraviolet absorbers are preferred from the viewpoint of imparting weather resistance, design properties, suppression of bleeding, and the like.

As the triazine-based ultraviolet absorber, the triazine-based ultraviolet absorber described in the above-mentioned primer for adhesion can be appropriately selected and used.

In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton can be used. Alternatively, an inorganic ultraviolet absorber may be added in the case where high transparency is not required. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, iron oxide, etc. having a particle size of 0.2 μm or less can also be used.

The content of the ultraviolet absorber can be appropriately determined in accordance with the ultraviolet absorbing ability of the ultraviolet absorber to be used.

When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, the adhesive layer preferably contains 0.5 mass% to 2 mass%.

When the content of the adhesive layer is less than 0.5% by mass, weather resistance may not be sufficiently imparted, and when the content of the adhesive layer exceeds 2% by mass, transparency of the adhesive layer may be impaired to lower design properties of the decorative sheet, or adhesion between the pattern layer and a transparent resin film described later may not be sufficiently obtained to lower suitability for processing of the decorative sheet of the present invention.

The content of the ultraviolet absorber is more preferably 1 mass% to 1.5 mass%.

[ method for producing decorative plate ]

Examples of the method for producing the decorative sheet of the present invention include a method in which the base material, the pattern layer and the transparent resin film are laminated by a heat-melting method or a heat lamination method, and further by using a hot-melt adhesive, a heat-sensitive adhesive, a pressure-sensitive adhesive, a hot-melt adhesive, an adhesive for forming the adhesive layer, or the like, in addition to an aqueous adhesive, a heat-sensitive adhesive, or a pressure-sensitive adhesive.

Among them, it preferably includes: forming the adhesive layer on a surface of the transparent resin film on which the pattern layer is laminated; and a step of bonding the transparent resin film and the pattern layer via the adhesive layer.

Such a method of manufacturing the decorative sheet of the present invention is also an embodiment of the present invention.

In the method for manufacturing a decorative sheet of the present invention, it is possible to prevent air from entering into the uneven shape formed on the transparent resin film on the side where the pattern layer is laminated, that is, to prevent so-called air inclusion from occurring, and to suppress a reduction in design of the pattern layer.

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

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

(example 1)

A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to one surface of the transparent polypropylene film to obtain an adhesive primer layer having a thickness of 2 μm. Next, a transparent polypropylene resin (80 μm thick) was melt-extruded on the other surface of the transparent polypropylene film (the opposite surface side of the adhesive primer layer), and these were laminated by heat lamination.

After the surface (opposite side to the adhesive primer) of the transparent polypropylene resin (80 μm in thickness) was subjected to corona treatment, a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to form a primer layer for a surface protective layer having a thickness of 2 μm.

Then, on the surface coated with the primer layer for surface protection layer, urethane acrylate oligomer as ionizing radiation curing resin was coated as a surface protection layer by gravure coating, and then, electron beams were irradiated under conditions of an accelerating voltage of 165keV and 5Mrad to form a surface protection layer having a thickness of 15 μm.

The surface-protecting layer side is heated by an infrared non-contact heater and then embossed by hot pressing to form a concave-convex shape, thereby forming a transparent resin film. The thickness of the obtained transparent resin film was 159. mu.m, the thickness of the concave portions of the uneven shape was 100. mu.m, and Rzmax was 40. mu.m.

On the other hand, an HDF (high density fiberboard) (thickness 3mm) was prepared, and a pattern layer having a thickness of 2 μm was provided on one side of the HDF by an ink jet printer, thereby preparing a base material.

The surface of the obtained transparent resin film having the adhesion primer layer was coated with a two-pack curable polyester resin containing isocyanate as a curing agent to form an adhesive layer having a thickness of 50 μm, and the adhesion primer layer of the transparent resin film obtained on the side was laminated in such a manner as to face the pattern layer. In this case, a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA) was added to the two-component curable polyester resin in an amount of 1 mass%.

Thereafter, 10kg/m was applied for 3 days²The pressure of (2) was maintained at a normal temperature to obtain a decorative sheet. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 2)

A decorative sheet was produced in the same manner as in example 1, except that a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) was added to the two-component curable polyester resin in an amount of 0.5 mass%. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 3)

A decorative sheet was produced in the same manner as in example 1, except that a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) was added to the two-component curable polyester resin in an amount of 2 mass%. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 4)

A transparent polypropylene film (thickness: 50 μm) was used instead of the transparent polypropylene film (thickness: 60 μm), and a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to one surface of the transparent polypropylene film (thickness: 50 μm) to obtain an adhesive primer layer having a thickness of 2 μm. Next, a transparent polypropylene resin (50 μm in thickness) was melt-extruded onto the other surface (the opposite surface side of the adhesive primer layer) of the transparent polypropylene film (50 μm in thickness), and these were laminated by a heat lamination method. After that, the primer layer for the surface protective layer and the surface protective layer were formed in the same manner as in example 1, and then embossed using a shallow embossing plate different from example 1, to obtain a transparent resin film.

The surface of the obtained transparent resin film having the adhesion primer layer was coated with a two-pack curable polyester resin containing isocyanate as a curing agent to form an adhesive layer having a thickness of 10 μm, and the adhesion primer layer and the pattern layer of the obtained transparent resin film were laminated so as to face each other.

A decorative sheet was produced in the same manner as in example 1 except for the above. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 5)

A decorative sheet was produced in the same manner as in example 4, except that a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) was added to the two-component curable polyester resin in an amount of 0.5 mass%. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 6)

A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to one surface of the transparent polypropylene film to obtain an adhesive primer layer having a thickness of 2 μm. Next, a transparent polypropylene resin (having a thickness of 60 μm) was melt-extruded onto the other surface of the transparent polypropylene film (the opposite surface side of the adhesive primer layer), and these were laminated by a thermal lamination method.

After that, the primer layer for the surface protective layer and the surface protective layer were formed in the same manner as in example 1, and then embossed using a shallow embossing plate different from example 1, to obtain a transparent resin film.

The surface of the obtained transparent resin film having the adhesion primer layer was coated with a two-pack curable polyester resin containing isocyanate as a curing agent to form an adhesive layer having a thickness of 40 μm, and the adhesion primer layer and the pattern layer of the obtained transparent resin film were laminated so as to face each other.

In this case, a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA) was added to the two-component curable polyester resin in an amount of 0.5 mass%.

A decorative sheet was produced in the same manner as in example 1 except for the above. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 7)

A decorative sheet was produced in the same manner as in example 1, except that the ultraviolet absorber added to the two-component curable polyester resin was changed to a benzotriazole-based ultraviolet absorber (product name: ADKSTAB LA-36, manufactured by ADEKA corporation). The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

Comparative example 1

A decorative sheet was produced in the same manner as in example 4, except that no ultraviolet absorber was added to the two-component curable polyester resin. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 8)

A transparent resin film and a decorative sheet were produced in the same manner as in example 4, except that embossing was performed using a deep embossing plate different from that of example 4. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 9)

Instead of the transparent polypropylene film (thickness: 60 μm), a transparent polypropylene film (thickness: 80 μm) was used, and a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to one surface of the transparent polypropylene film (thickness: 80 μm) to obtain an adhesive primer layer having a thickness of 2 μm. Next, a transparent polypropylene resin (having a thickness of 80 μm) was melt-extruded onto the other surface (the opposite surface side to the adhesive primer layer) of the transparent polypropylene film (having a thickness of 80 μm), and these were laminated by a heat lamination method. After that, the primer layer for the surface protective layer and the surface protective layer were formed in the same manner as in example 1, and then embossed by a deep embossing plate different from example 1, thereby obtaining a transparent resin film.

The surface of the obtained transparent resin film having the adhesion primer layer was coated with a two-pack curable polyester resin containing isocyanate as a curing agent to form an adhesive layer having a thickness of 100 μm, and the adhesion primer layer and the pattern layer of the obtained transparent resin film were laminated so as to face each other.

A decorative sheet was produced in the same manner as in example 2 except for the above. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 10)

On the surface of the transparent resin film obtained in the same manner as in example 4, which had the primer layer for adhesion, a two-pack curable polyester resin containing isocyanate as a curing agent was applied to form an adhesive layer having a thickness of 5 μm, and the primer layer for adhesion and the pattern layer of the obtained transparent resin film were laminated so as to face each other.

A decorative sheet was produced in the same manner as in example 4 except for the above. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 11)

A decorative sheet was produced in the same manner as in example 1, except that a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) was added to the two-component curable polyester resin in an amount of 3 mass%. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 1.

(example 12)

A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-pack type curable polyurethane resin containing 5 mass% of a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA) and using isocyanate as a curing agent was applied to one surface of the transparent polypropylene film to obtain an adhesive primer layer having a thickness of 2 μm. Next, a transparent polypropylene resin (having a thickness of 80 μm) was melt-extruded onto the other surface of the transparent polypropylene film (the opposite surface side to the adhesive primer), and these were laminated by a thermal lamination method.

The surface (opposite side to the adhesive primer) of the transparent polypropylene resin (80 μm) was subjected to corona treatment, and then a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to form a primer layer for a surface protective layer having a thickness of 2 μm.

Then, on the surface coated with the surface protective layer primer, urethane acrylate oligomer as an ionizing radiation curable resin was coated as a surface protective layer by a gravure coating method, and then an electron beam was irradiated under conditions of an accelerating voltage of 165keV and 5Mrad to form a surface protective layer having a thickness of 15 μm.

The surface-protecting layer side was heated by an infrared non-contact heater, and then embossed by hot pressing to form a concave-convex shape, thereby producing a transparent resin film. The thickness of the obtained transparent resin film was 159. mu.m, and the thickness of the concave portions having the irregular shape was 100. mu.m.

On the other hand, an HDF (high density fiberboard) (thickness 3mm) was prepared, and a pattern layer having a thickness of 2 μm was provided on one side of the HDF by an ink jet printer, thereby preparing a base material.

The surface of the obtained transparent resin film having the adhesion primer layer was coated with a two-pack curable polyester resin containing isocyanate as a curing agent to form an adhesive layer having a thickness of 30 μm, and the adhesion primer layer of the obtained transparent resin film and the pattern layer were laminated so as to face each other. Thereafter, 10kg/m was applied for 3 days²The pressure of (2) was maintained at a normal temperature to obtain a decorative sheet. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(examples 13 to 14)

A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that the content of the triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) added to the primer layer for adhesion was changed to 1 mass% (example 13) or 10 mass% (example 14). The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(example 15)

A two-pack type curable polyurethane resin (0.5 μm in thickness) containing 1 mass% of a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA) and an isocyanate as a curing agent was applied to one surface of a transparent polypropylene film (60 μm) to form an adhesive primer layer. A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that a transparent polypropylene resin (thickness 60 μm) was extruded instead of the transparent polypropylene resin (thickness 80 μm) and laminated by heat lamination, on the other surface of the transparent polypropylene film (thickness 60 μm). The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(example 16)

A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that the thickness of the adhesion primer layer was set to 10 μm. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(example 17)

A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that a triazine-based ultraviolet absorber (product name: ADKSTAB LA-46, manufactured by ADEKA corporation) was added in an amount of 1 mass% to a two-pack curable polyester resin (thickness: 50 μm) having isocyanate as a curing agent as an adhesive layer. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(example 18)

A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that the ultraviolet absorber added to the adhesive base coat layer was changed to a benzotriazole-based ultraviolet absorber (product name: ADKSTAB LA-36, manufactured by ADEKA corporation). The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

Comparative example 2

A transparent resin film and a decorative sheet were produced in the same manner as in example 15, except that no ultraviolet absorber was added to the adhesive base coat layer. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

(example 19)

A transparent resin film and a decorative sheet were produced in the same manner as in example 12, except that the thickness of the adhesive base coat was changed to 13 μm. The thickness of the obtained transparent resin film and the thickness of the concave portions in the uneven shape are shown in table 2.

< determination of Rzmax >

Rzmax defined in JIS B0601(2001) of the uneven shape on the side of the pattern layer of the transparent resin film in the decorative sheets obtained in examples 1 to 19 and comparative examples 1 and 2 was measured under the following conditions using a surface roughness measuring instrument ("SURFCOM-FLEX-50A", manufactured by tokyo kokai).

(measurement conditions)

The number of times of measurement: n-5 (arbitrary 5 dots)

Calculating a standard: JIS' 01

The measurement types are as follows: roughness measurement

Evaluation length: 12.5mm

Cutoff value: 2.5mm

Measuring speed: 0.60mm/s

Filter type: gauss type

Shape removal: straight line

λ s value: 8.0 μm

When the uneven shape has directionality, the flow direction and the direction perpendicular thereto are measured, and the larger value of the two is taken as Rzmax.

(evaluation method)

< abrasion resistance (Taber Friction test) >

For the decorative boards obtained in examples 1 to 19 and comparative examples 1 and 2, reference was made to the japanese agro-forestry standard for wood flooring; the friction A test was conducted under a load of 1kg using a Taber type friction tester (manufactured by Kimura Kogyo Co., Ltd.) and a friction wheel (S-42), and the pattern residual amount of the pattern layer was evaluated at 1000 revolutions. The results are shown in tables 1 and 2.

++: more than 80% of pattern layer residue

+: more than half of the pattern layer is remained but less than 80 percent

-: less than half of the pattern layer residue

Color difference after weather resistance test

The decorative sheets obtained in examples 1 to 19 and comparative examples 1 and 2 were put into an ultra-accelerated weathering tester (EYE Super UV tester manufactured by Kawasaki electric Co., Ltd.) set to the following conditions, and subjected to 1 cycle of 20-hour irradiation and 4-hour condensation, and then subjected to 17 cycles of operation, and then taken out.

(accelerated test conditions)

Black panel temperature: 63 deg.C

Humidity: 50% RH

Irradiation intensity: 60W/m²(365nm)

Then, the change in color difference of the decorative sheet before and after the accelerated test was measured by a color difference meter (CR-300, manufactured by Meinenda corporation). That is, the L value, a value, and b value of the decorative sheet before and after the accelerated test were measured, and the color difference change Δ E was calculated by the following formula 1. The results are shown in tables 1 and 2.

ΔE＝[(ΔL)²+(Δa)²+(Δb)²]^1/2Formula 1

++：ΔE＜1.0

+：1.0≤ΔE＜1.5

－：ΔE≥1.5

Δ L ═ L value (after weathering test) -L value (before weathering test) |

Δ a ═ a value (after weathering test) -a value (before weathering test) |

Δ b ═ a value (after weathering test) -a value (before weathering test) |

< design of appearance >

The decorative sheets obtained in examples 1 to 19 and comparative examples 1 and 2 were evaluated for the printed pattern by visual observation. The results are shown in tables 1 and 2.

+++: the printed pattern is clearly visible

++: slightly blurred printed pattern

+: the printed pattern is slightly yellow

-: the printed pattern is not clearly seen

< membrance >

In examples 12 to 19 and comparative example 2, it was confirmed that the obtained transparent resin films had no defects (blocking) during production, and the film formability was evaluated. The results are shown in Table 2.

++: no adhesion

+: only some adhesion

-: adhesion occurs

< manufacturing suitability (sealing strength) >

In examples 1 to 19 and comparative examples 1 and 2, adhesion strength was evaluated when the obtained transparent resin films were laminated so that the surface opposite to the surface having the uneven shape was in contact with the surface of the substrate having the pattern layer. The results are shown in tables 1 and 2.

++: sealing without any problem (sealing strength exceeding 20N/25mm)

+: slightly weak adhesion strength (adhesion strength of 15N/25mm or more and 20N/25mm or less)

-: the sealing strength was very weak (sealing strength was less than 15N/25mm)

The maximum value of the peel strength [ N/25mm width ] when the transparent resin film was peeled from the substrate on which the pattern layer was laminated was measured as the adhesive strength at a tensile speed of 200mm/min and a peel angle of 180 DEG using a Tensilon Universal test machine "RTC-1250A" (manufactured by ORIENTEC corporation).

[ Table 1]

[ Table 2]

As can be seen from Table 1, the decorative sheets obtained in examples 1 to 11 were excellent in weather resistance.

In particular, examples 1 to 6, in which the thickness of the concave portions of the uneven shape of the transparent resin film, Rzmax, and the thickness of the adhesive layer were in predetermined ranges and the triazine-based ultraviolet absorber was used, were excellent in all of the abrasion resistance, the design property, and the processability.

On the other hand, in example 7 in which a benzotriazole-based ultraviolet absorber was used as an ultraviolet absorber, yellowing occurred, and the appearance design was slightly poor, and the processability was also poor. In example 8 in which the recesses in the uneven shape of the transparent resin film were less than 80 μm, the abrasion resistance was poor. In example 9 in which Rzmax of the transparent resin film exceeded 80 μm and example 10 in which the adhesive layer had a thickness of less than 10 μm, the appearance was poor because of air entrapment. In example 11 in which the adhesive layer contained 3 mass% of the ultraviolet absorber, the transparency was lowered and the appearance design was poor.

In comparative example 1 having no layer containing an ultraviolet absorber, the weather resistance was poor.

As can be seen from Table 2, the decorative sheets obtained in examples 12 to 19 were excellent in weather resistance.

In particular, in examples 12 to 17 in which the thickness of the concave portions of the uneven shape of the transparent resin film was in a predetermined range, the thickness of the adhesion primer layer was in a predetermined range, and the triazine-based ultraviolet absorber was used, the abrasion resistance, the design property, the film forming property, and the processing suitability were excellent.

On the other hand, in example 18 in which a benzotriazole-based ultraviolet absorber was used as an ultraviolet absorber, yellowing occurred, and the appearance design was slightly poor. In example 19 in which the thickness of the adhesive primer layer exceeded 10 μm, the transparency was reduced and the design was poor.

In comparative example 2 having no layer containing an ultraviolet absorber, the weather resistance was poor.

Industrial applicability

According to the present invention, a decorative sheet having excellent weather resistance can be provided. The decorative sheet of the present invention is also excellent in weather resistance, and therefore is preferably used as a building material for doors, windows, sliding doors, and other doors, floor materials, walls, roofs, and various decorative molded articles.

Description of the symbols:

10 decorative boards; 11 a substrate; 12 a pattern layer; 13 an adhesive layer; 20 a transparent resin film; 21 a primer layer for adhesion; 22 a thermoplastic resin layer; 23 a primer layer for a surface protective layer; 24 a surface protection layer.