阅读说明：本技术 透明性树脂膜、装饰板和装饰板的制造方法 (Transparent resin film, decorative sheet, and method for producing decorative sheet ) 是由 藤井亮 古田哲 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：本发明提供一种能够对装饰板赋予优异的设计性、与图案层的密合性能也优异的透明性树脂膜、使用该透明性树脂膜得到的装饰板以及该装饰板的制造方法。本发明涉及用于保护在基材的一侧叠层的图案层的透明性树脂膜,该透明性树脂膜的特征在于,在上述透明性树脂膜的叠层上述图案层的一侧具有凹凸形状,该凹凸形状的JIS B 0601(2001)所定义的最大高度粗糙度Rz为15μm以上70μm以下的范围。(The invention provides a transparent resin film which can endow a decorative plate with excellent design and excellent adhesion performance with a pattern layer, a decorative plate obtained by using the transparent resin film and a manufacturing method of the decorative plate. The present invention relates to a transparent resin film for protecting a pattern layer laminated on one side of a substrate, the transparent resin film being characterized in that the transparent resin film has an uneven shape on the side where the pattern layer is laminated, and the uneven shape has a maximum height roughness Rz defined in JIS B0601(2001) in a range of 15 to 70 μm.)

1. A transparent resin film for protecting a pattern layer laminated on one side of a substrate, the transparent resin film characterized in that:

the transparent resin film has an uneven shape on the side where the pattern layer is laminated, and the maximum height roughness Rz of the uneven shape defined in JIS B0601(2001) is in the range of 15 to 70 [ mu ] m.

2. The transparent resin film according to claim 1, wherein:

the transparent resin film has an uneven shape on the side opposite to the side on which the pattern layer is laminated, and the maximum height roughness Rz of the uneven shape defined in JIS B0601(2001) is in the range of 30 to 100 [ mu ] m.

3. The transparent resin film according to claim 1 or 2, wherein:

the transparent resin film has an adhesive primer layer on the side where the pattern layer is laminated.

4. The transparent resin film according to claim 1, 2 or 3, wherein:

the transparent resin film has a surface protective layer on the side opposite to the side on which the pattern layer is laminated.

5. A decorative panel, characterized in that:

a transparent resin film according to claim 1, 2, 3 or 4, which comprises a substrate, a pattern layer and the resin film in this order in the thickness direction.

6. A manufacturing method of a decorative panel for manufacturing the decorative panel of claim 5, characterized by 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 to the pattern layer via the adhesive layer.

Technical Field

The present invention relates to a transparent resin film, a decorative sheet obtained using the transparent resin film, and a method for producing the decorative sheet.

Background

In recent years, due to the widespread use of an ink jet printing method using an ink jet printer, decorative sheets used for building materials, decorative molded articles, and the like can be applied to various types and small lots, and complicated patterns (characters, numerals, figures, and the like) can be printed as a pattern layer.

Further, the substrate printed by the inkjet printing method is not limited to a film, and there is an advantage that printing can be performed also on a flat plate or a substrate having an uneven or curved surface.

However, since the pattern layer printed by the inkjet printing method is usually located on the outermost surface of the substrate, surface properties such as scratch resistance, stain resistance, and weather resistance are insufficient, and a transparent resin film needs to be laminated on the surface of the pattern layer in order to protect the pattern layer.

For example, patent document 1 discloses a technique of laminating a transparent resin layer and a transparent protective layer on the surface of a pattern layer to alleviate or eliminate defects such as unevenness and scratches generated on a decorative sheet, and providing an uneven pattern on the surface of the decorative sheet to present a design similar to an actual wood grain.

However, conventionally, there has been a problem in adhesion between a pattern layer and a transparent resin film laminated on a surface of the pattern layer, and there has been room for improvement.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-74682

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a transparent resin film with excellent design and excellent adhesion with a pattern layer, a decorative sheet obtained by using the transparent resin film and a manufacturing method of the decorative sheet.

Technical solution for solving technical problem

In order to solve the above-described problems, the present inventors have conducted extensive studies with attention paid to the shape of the surface of the transparent resin film laminated on one side of the pattern layer. As a result, the present inventors have found that a predetermined uneven shape is formed on the surface of the transparent resin film laminated on the pattern layer side, whereby the adhesion area (surface area) of the adhesive layer provided between the transparent resin film and the pattern layer can be increased, and a transparent resin film having excellent adhesion to the pattern layer and excellent design properties can be obtained, thereby completing the present invention.

The present invention is a transparent resin film for protecting a pattern layer laminated on one side of a substrate, characterized in that the transparent resin film has an uneven shape on the side where the pattern layer is laminated, and the maximum height roughness Rz of the uneven shape defined in JIS B0601(2001) is in the range of 15 [ mu ] m to 70 [ mu ] m.

The transparent resin film of the present invention preferably has an uneven shape on the side opposite to the side on which the pattern layer is laminated, and the maximum height roughness Rz of the uneven shape defined in JIS B0601(2001) is in the range of 30 μm to 100 μm.

In addition, the transparent resin film of the present invention preferably has an adhesion primer layer on the side where the pattern layer is laminated.

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

The present invention is also a decorative sheet comprising a base material, a pattern layer and the transparent resin film of the present invention in this order in the thickness direction.

The present invention is also a method for manufacturing a decorative sheet of the present invention, the method comprising: 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 to the pattern layer via the adhesive layer.

Effects of the invention

The invention provides a transparent resin film which can endow a decorative plate with excellent design and has excellent adhesion with a pattern layer.

The decorative sheet of the present invention obtained using the transparent resin film of the present invention has excellent design properties and excellent adhesion to the pattern layer.

Drawings

Fig. 1 is a schematic cross-sectional view showing a preferred example of the transparent resin film of the present invention.

Fig. 2 is a schematic view showing a cross section of another preferred example of the transparent resin film of the present invention.

Fig. 3 is a schematic cross-sectional view showing a preferred example of the decorative sheet of the present invention.

Detailed Description

First, the transparent resin film of the present invention will be explained.

The transparent resin film of the present invention has a predetermined uneven shape on one surface (hereinafter also referred to as an adhesive surface) laminated on the pattern layer, and therefore, when laminated on the pattern layer via the adhesive layer, the adhesive area between the adhesive layer and the adhesive surface increases, and adhesion is excellent.

A preferred example of the transparent resin film of the present invention will be described with reference to fig. 1.

As shown in fig. 1, the transparent resin film 10 of the present invention has a concavo-convex shape on a surface (adhesive surface) B laminated on one side of the pattern layer.

In the transparent resin film 10 of the present invention, the maximum height roughness Rz defined in JIS B0601(2001) of the uneven shape of the bonding surface B is in the range of 15 μm to 70 μm. If Rz is less than 15 μm, the effect of improving adhesion when the adhesive layer is provided cannot be sufficiently obtained, and if it exceeds 70 μm, air bubbles enter between the adhesive layer and the uneven shape when the adhesive layer is provided, and the design property is lowered. The Rz of the adhesive surface B has a preferable lower limit of 20 μm and a preferable upper limit of 65 μm, a more preferable lower limit of 25 μm and a more preferable upper limit of 60 μm.

The maximum height roughness Rz of the bonding surface B can be measured by a surface roughness meter (product name SURFCOM FLEX-50A, manufactured by tokyo co., ltd.) in accordance with JIS B0601(2001), for example.

The transparent resin film 10 of the present invention has a concavo-convex shape on a surface (hereinafter also simply referred to as surface) a on the side opposite to the side on which the pattern layer is laminated, and preferably has a maximum height roughness Rz defined in JIS B0601(2001) of the concavo-convex shape in a range of 30 μm to 100 μm. If the Rz of the surface is less than 30 μm, the low gloss feeling and the touch may be lowered, while if the Rz of the surface exceeds 100 μm, the transmittance may be lowered, and the visibility of the pattern layer may be lowered.

A more preferable lower limit of Rz of the surface is 35 μm, and a more preferable upper limit is 95 μm.

The method for forming the uneven shape on the surface a and the adhesive surface B of the transparent resin film of the present invention is not particularly limited, and examples thereof include embossing by heat, and a method of transferring the uneven shape by a shaping sheet.

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

Examples of the embossed pattern include sand lines, hair lines, pear peel patterns, wood grain board guide grooves, stone board surface irregularities, cloth surface textures, and ruled line grooves.

The temperature at which the embossing is performed is not particularly limited, but is preferably a temperature at which so-called emboss recovery reduction, in which the uneven pattern disappears, is achieved during the heat pressure bonding molding.

In addition, the concave-convex shape may be formed on both surfaces of the transparent resin film by the above method, or the concave-convex shape may be formed on one surface of the transparent resin film by the above method, and the concave-convex shape on the other surface may be formed so as to follow the concave-convex shape formed on the one surface.

The thickness of the transparent resin film is not particularly limited, and 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, sufficient durability (abrasion resistance and scratch resistance) may not be imparted to the transparent resin film of the present invention.

The "concave and convex shaped recesses" are the thinnest portions of the transparent resin film of the present invention, and as shown in fig. 1, the portions including the deepest concave and convex shaped recesses of the transparent resin film 10 of the present invention can be confirmed by observing the cross section of the transparent resin film of the present invention through a microscope. Further, the length from the bottom of the deepest recessed portion to the bonding surface B is "the thickness of the recessed portion having a concave-convex shape", and for example, as shown in fig. 1, when a protruding portion corresponding to the concave-convex shape is formed on the bonding surface B, the length from the bottom of the deepest recessed portion to the protruding portion of the bonding surface B of the transparent resin film 10 of the present invention is "the thickness of the recessed portion having a concave-convex shape".

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

As shown in fig. 1, the length from the surface a to the adhesive surface B (to the protruding portion when the protruding portion is formed) of the transparent protective film of the present invention is the total thickness of the transparent resin film 10 of the present invention, and the total thickness preferably has a lower limit of 60 μm and an upper limit of 500 μm, more preferably has a lower limit of 100 μm and a more preferably upper limit of 460 μm.

Next, another preferred example of the transparent resin film of the present invention will be described with reference to fig. 2.

As shown in fig. 2, the transparent resin film 10 of the present invention preferably includes a thermoplastic resin layer 14 and a surface protective layer 13 stacked thereon, and an adhesion primer layer 12 on the side opposite to the side having the thermoplastic resin layer 14 and the surface protective layer 13.

In the transparent resin film 10 of the present invention, the adhesive primer layer 12 is provided on the side of the pattern layer, so that the adhesion to the pattern layer is strong, and from such a viewpoint, it is preferable that the pattern layer and the adhesive primer layer 12 are laminated to face each other.

Hereinafter, each structure of the transparent resin film of the present invention will be described.

In addition, from the viewpoint of securing the adhesion between the thermoplastic resin layer 14 and the surface protective layer 13, it is preferable to provide an undercoat layer for surface protective layer (not shown) between these layers.

In the following description, the adhesive primer layer 12 and the surface protective layer primer layer will be collectively referred to as "primer layers".

The thermoplastic resin layer is a layer that functions to protect the pattern layer, and the thermoplastic resin layer may be translucent or colored as long as it is transparent, within a range in which the pattern layer described later can be visually recognized.

The thermoplastic resin includes the following 1 or more resins, and examples thereof include: olefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, and olefin-based thermoplastic elastomers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-ethylene glycol-1, 4-cyclohexanedimethanol copolymer, and polyester thermoplastic elastomers; acrylic resins such as polymethyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymers, and methyl (meth) acrylate-styrene copolymers; polycarbonate resins, polyvinyl chloride, polystyrene, ionomers, and the like. Among them, polypropylene is preferably used from the viewpoint of high tensile strength and excellent drug resistance.

Wherein, in the present specification, (meth) acrylate means acrylate or methacrylate.

The thermoplastic resin layer may be an unstretched layer or a layer 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, 500 μm at the upper limit, 60 μm at the lower limit, and 420 μm at the upper limit. If the thickness of the thermoplastic resin layer is less than 20 μm, the strength may be insufficient to protect the surface of the pattern layer, and if it exceeds 500 μm, the transmittance of the transparent resin film may be lowered, thereby deteriorating the visibility of the pattern layer.

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

When the thermoplastic resin layer is composed of a plurality of types of resins, the types of resins forming the base material composed of the plurality of types of resins may be the same or different, and the thicknesses of the base materials composed of the plurality of types of resins may be the same or different.

The method of laminating 2 or more thermoplastic resin layers is not limited as long as it is a general method, and a dry lamination method, an extrusion thermal lamination method, or 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, and flame treatment without departing from the scope of the present invention.

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

The surface protective layer is a layer that imparts excellent durability (scratch resistance, stain resistance, weather resistance, and the like) to the transparent resin film of the present invention, and can more suitably protect the surface of the pattern layer, and can suitably prevent a reduction in design properties due to scratching of the transparent resin film of the present invention itself.

The surface protection layer may be a single layer, may be a multilayer structure composed of the same or different materials, or may be a mixture of the following materials.

The surface protective layer is not particularly limited, and examples thereof include a layer formed of a crosslinked cured product of a two-liquid curable resin or an ionizing radiation curable resin composition, and the crosslinked cured product is preferably transparent, may be translucent, and may be colored within a range in which the pattern layer described below can be visually recognized.

As the two-liquid curable resin, a binder resin of an undercoat layer described later can be used.

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 means an electromagnetic wave or a charged particle having energy capable of polymerizing or crosslinking a molecule, and is generally an Electron Beam (EB) or ultraviolet ray (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, and a cation polymerizable functional group such as an epoxy group in the molecule. These oligomers and monomers may be used alone or in combination. Wherein, in the present specification, the above (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 is preferably used, and a urethane (meth) acrylate oligomer is more preferably used. As the molecular weight, about 250 to 10 ten thousand oligomers can be usually used.

The monomer having a radical polymerizable unsaturated group in the molecule is preferably 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 the ionizing radiation curable resin component is particularly preferably a urethane acrylate oligomer/polyfunctional monomer (mass ratio) of 6/4 to 9/1. When within this mass ratio range, the scratch resistance is more excellent.

Further, if necessary, a monofunctional monomer may be appropriately used 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, the photopolymerization initiator may be acetophenone, benzophenone, thioxanthone, benzoin, and benzoin methyl ether, either alone or in combination.

In the case where the ionizing radiation-curable resin composition is a resin system having 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 further added to the ionizing radiation curable resin composition as needed. Examples of such 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 copolymers, vinyl acetate resins, acrylic resins, and cellulose resins; lubricants such as silicone resins, waxes, fluorine-containing resins, and the like; ultraviolet absorbers such as benzotriazole, benzophenone, and triazine; light stabilizers such as hindered amine radical scavengers; colorants such as dyes and pigments.

Further, as the electron beam source of the ionizing radiation, for example, a source which irradiates electrons having an energy of 70 to 1000keV with various electron beam accelerators of the kochrowatt-walton type, van der graff type, resonance transformer type, insulation core transformer type, linear type, high frequency high voltage type, high frequency type, and the like can be used. The dose of the electron beam is, for example, about 1 to 10 Mrad.

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

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. If the thickness of the surface protective layer is less than 0.1 μm, sufficient durability (scratch resistance, stain resistance, weather resistance, etc.) may not be imparted, and if it exceeds 50 μm, the transmittance of the transparent resin film of the present invention may be reduced, resulting in a reduction in visibility of the pattern layer.

The primer layer (the primer layer 12 for adhesion and the primer layer for surface protection layer) preferably contains a binder resin.

Examples of the binder resin contained in the undercoat layer include urethane resin, acrylic-urethane copolymer, cellulose resin, polyester resin, vinyl chloride-vinyl acetate copolymer, and the like. 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 between the pattern layer and the transparent resin film described later and efficiency in production.

The undercoat layer preferably contains an ultraviolet absorber.

Particularly, when the adhesive primer layer 12 contains an ultraviolet absorber, the decorative sheet of the present invention can be appropriately 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: 2 ' -hydroxyphenyl-5-chlorobenzotriazole ultraviolet absorbers such as 2- (2 ' -hydroxy-3 ', 5 ' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -tert-amyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-3 ' -isobutyl-5 ' -propylphenyl) -5-chlorobenzotriazole and the like; benzotriazole-based ultraviolet absorbers such as 2 '-hydroxyphenylbenzotriazole-based ultraviolet absorbers (e.g., 2- (2' -hydroxy-3 ', 5' -di-tert-butylphenyl) benzotriazole and 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole); 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, and 2-hydroxybenzophenone-based ultraviolet absorbers including 2-hydroxy-4-methoxybenzophenone and 2, 4-dihydroxybenzophenone; salicylate-based ultraviolet absorbers such as phenyl salicylate and 4-tert-butylphenyl salicylate.

Among them, triazine-based ultraviolet absorbers are preferable from the viewpoint of appropriately imparting weather resistance, design properties, barrier properties, 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-triyltrimethylamino) tribenzoic acid tris (2-ethylhexyl ester), 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1, 3, 5-triazine, N' -tri-m-tolyl-1, 3, 5-triazine-2, 4, 6-triamine, 2,4, 6-tris (4-butoxy-2-hydroxyphenyl) -1, 3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ 2- (2-ethylhexanoyloxy) ethoxy ] phenol, and the like.

In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton, or the like can be used. Alternatively, in the case where high transparency is not required, an inorganic ultraviolet absorber may be added. 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 in the undercoat layer may be appropriately determined so as to achieve the above ultraviolet transmittance range, depending on the ultraviolet absorbing ability of the ultraviolet absorber used.

When a triazine-based ultraviolet absorber is used as the ultraviolet absorber, the content of the primer layer is preferably 1 to 10% by mass, more preferably 2% by mass or more and 7% by mass or less. If the amount is less than 1% by mass, the weather resistance may not be sufficiently imparted, and if the amount exceeds 10% by mass, the design of the transparent resin film of the present invention may be deteriorated, or the film-forming and processing properties may be deteriorated.

The thickness of the primer layer is preferably 0.5 μm to 10 μm. When the thickness is 0.5 μm or more, the adhesion between the transparent resin film of the present invention and the pattern layer and the surface protective layer to be described later can be suitably ensured, and when the thickness is 10 μm or less, the thickness of the transparent resin film of the present invention is preferably not too large.

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

The transparent resin film of the present invention is used for protecting a pattern layer laminated on one surface of a base material, and has a predetermined uneven shape on an adhesive surface, and therefore, when the pattern layer is laminated with the transparent resin film of the present invention through the adhesive layer to form a decorative sheet, the decorative sheet has excellent adhesion performance, and air bubbles do not enter the uneven shape, and thus, the decorative sheet has excellent design properties.

Such a decorative sheet in which a pattern layer is laminated on one surface of a base material and the transparent resin film of the present invention is laminated on the side opposite to the side having the base material of the pattern layer is also one embodiment of the present invention.

Next, a preferred example of the decorative sheet of the present invention will be described with reference to fig. 3.

In the decorative sheet 20 of the present invention, the pattern layer 24 is laminated on one surface of the base material 25, and the transparent resin film 10 of the present invention is laminated on the side of the pattern layer 24 opposite to the side having the base material 25.

In addition, the adhesive layer 23 is preferably provided in order to further secure the adhesion between the pattern layer 24 and the transparent resin film 10 of the present invention.

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

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

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

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

As the thermoplastic resin, preferred are: polyvinyl resins such as polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol resin; polyolefin resins such as polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene- (meth) acrylic acid resins; polyester resins such as polyethylene terephthalate resins (PET resins); monomers and copolymers of thermoplastic resins such as acrylic resins, polycarbonate resins, polyurethane resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), acrylonitrile-styrene copolymers, and the like; or a mixed resin thereof. Among them, polyolefin resins, acrylonitrile-butadiene-styrene copolymers, polyvinyl chloride resins, ionomers, and the like are preferable. In addition, the resin material may be foamed.

Examples of the wood material include various raw materials such as cedar, cypress, beech, pine, eucalyptus, teak, and horse-chest wood, and the core material may be any of a flat cut veneer, a wood plywood (including LVL), a particle board, a Medium Density Fiberboard (MDF), a High Density Fiberboard (HDF), and an integrated material produced from these raw materials, and a laminate material obtained by appropriately laminating these materials.

Examples of the metal material include iron.

The base material may contain an inorganic compound.

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

In the present invention, the substrate may have a hollow structure, a slit groove or a through hole may be formed in a part of the substrate, or a frame-shaped substrate in which the above materials are combined.

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

The substrate also includes a substantially plate-shaped substrate, and also includes a substrate having irregularities or curved surfaces.

The substrate is laminated with a pattern layer on one surface.

The pattern layer is a layer for imparting decorativeness to the decorative sheet of the present invention obtained using the transparent resin film of the present invention, and may be, for example, a masking layer (entire surface printing layer) uniformly colored, a pattern layer formed by printing various patterns using ink or a printing machine, or a layer obtained by combining a masking layer and a pattern layer (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 performing an intended tint.

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

As the ink composition used for the pattern layer, a binder resin may be used 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. The binder resin is not particularly limited, and examples thereof include a urethane resin, an acrylic-urethane copolymer resin, a vinyl chloride/vinyl acetate/acrylic copolymer resin, an acrylic resin, a polyester resin, and a nitrocellulose resin. As the binder resin, any 1 of them may be used alone or 2 or more may be used in combination.

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

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. When the thickness of the pattern layer is within the above range, excellent design properties can be imparted to the decorative sheet of the present invention, and a masking property can also be imparted.

In addition, when the base material itself has design properties in advance, such as a flat cut veneer, the pattern layer may not be provided.

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.

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

The adhesive layer is provided between the pattern layer and the thermoplastic resin layer of the transparent resin film of the present invention, and by having the adhesive layer, the adhesion between the pattern layer and the transparent resin film of the present invention can be further strengthened.

In addition, since the transparent resin film of the present invention has a predetermined uneven shape formed on the surface (adhesive surface) on the pattern layer side, the adhesive area of the adhesive layer to the adhesive surface is increased, and as a result, the adhesive layer has excellent adhesion performance. Further, since the uneven shape is controlled to a predetermined shape, air bubbles can be prevented from entering between the adhesive layer and the uneven shape.

From the viewpoint of imparting more excellent weather resistance to the decorative sheet of the present invention, it is preferable that the adhesive layer contains an ultraviolet absorber.

Specifically, the adhesive layer preferably contains 0.5 to 2 mass% of an ultraviolet absorber. By containing the ultraviolet absorber in the above range, more excellent weather resistance can be imparted to the decorative sheet of the present invention.

The adhesive layer preferably contains 1.0 to 1.5 mass% of an ultraviolet absorber.

As the ultraviolet absorber contained in the adhesive layer, the ultraviolet absorber used in the primer layer can be suitably used, and a triazine-based ultraviolet absorber is particularly preferably used.

The adhesive layer preferably contains a binder resin.

As the binder resin contained in the adhesive layer, the binder resin used in the primer layer can be suitably used.

The method for producing the decorative sheet of the present invention may include a method of laminating the base material, the pattern layer, and the transparent resin film by using an adhesive or the like for forming the adhesive layer.

Among them, in the above method for manufacturing a decorative sheet, it is preferable that the method includes: forming an 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.

This method of manufacturing the decorative panel of the present invention is also one of the modes of the present invention.

In the transparent resin film, when the surface-protecting layer side is provided with the uneven shape, the uneven shape is formed by embossing or the like, but the uneven shape is also provided to some extent on the surface (the side on which the pattern layer is laminated) opposite to the surface subjected to embossing following the uneven shape on the side on which the embossing is performed. In this case, air enters the uneven shape on the side where the pattern layer is laminated, which is formed by the transparent resin film, and so-called air entrainment occurs, and the design may be degraded.

The method for manufacturing a decorative sheet according to the present invention includes a step of forming an adhesive layer on the surface of the transparent resin film on the side where the pattern layer is laminated, and therefore the adhesive layer can be made to enter the concave portions of the uneven shape on the side where the pattern layer is laminated, and the occurrence of the air entrainment can be prevented, and the reduction in design can be suppressed.

Examples

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

(example 1)

A transparent polypropylene film (thickness: 60 μm) was prepared, and a two-pack 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 (200 μm in thickness) was melt-extruded onto the other surface of the transparent polypropylene film (the surface opposite to the adhesive primer layer), and these were laminated by a heat lamination method to obtain a thermoplastic resin layer.

Then, the surface of the thermoplastic resin layer on the side of the transparent polypropylene resin (thickness: 200 μm) was subjected to corona treatment, and then a two-pack type curable polyurethane resin containing isocyanate as a curing agent was applied to obtain a primer layer for a surface protective layer having a thickness of 2 μm.

Then, on the surface of the surface protective layer primer layer, urethane (meth) acrylate as an ionizing radiation curable resin was applied 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.

Heating the surface protection layer side with an infrared non-contact heaterThen, the plate was brought into contact with an embossing plate (Rz: 25.1 μm) at 120 ℃ under a pressure of 55kg/cm²The pressure was applied for 180 seconds to impart a concavo-convex shape to obtain a transparent resin film.

On the other hand, an HDF (thickness 3mm) was prepared, and a pattern layer was applied to one surface of the HDF so as to have a thickness of 2 μm by an ink jet printer to prepare a substrate.

The adhesive base coat side of the obtained transparent resin film was coated with a two-pack curable polyester resin (thickness: 50 μm) containing isocyanate as a curing agent to form an adhesive layer, and the adhesive base coat side of the transparent resin film and the pattern layer side of the base material were laminated to each other at a rate of 10kg/m²The pressure of (3) is maintained for 3 days in a normal temperature environment.

The thickness of the concave portions in the uneven shape of the transparent resin film is shown in table 1.

(examples 2 to 6, comparative examples 1 and 2)

A transparent resin film and a decorative sheet were produced in the same manner as in example 1, except that the embossing plate was changed so that the uneven shape of the surface and the adhesive surface was changed to the size shown in table 1. The thickness of the concave portions in the uneven shape of the transparent resin film is shown in table 1.

The ratio of the bonding area to comparative example 1 shown in table 1 was determined as follows: the surface area of the surface of the transparent resin film on which the adhesive primer layer was formed in examples 1 to 6 and comparative example 2, and comparative example 1 was determined by measuring Sdr by using a roughness profile measuring machine (product name One Shot 3D profilometer VR-3200, manufactured by kirnshi limited) in a wide-angle view mode and a 15-type monitor magnification of 25 (12 mm in the horizontal direction (H) and 9mm in the vertical direction (V)) based on ISO 25178 and obtaining Sdr by [ (Sdr on the surface on which the primer layer was formed in examples 1 to 6 or comparative example 2)/(Sdr on the surface on which the primer layer was formed in comparative example 1) ].

< sealing Strength >

In the examples and comparative examples, the surface of the transparent resin film obtained on the side opposite to the side having the uneven shape was laminated in contact with the surface of the substrate having the pattern layer, and the adhesion strength at this time was evaluated. The results are shown in table 1.

The adhesion strength was measured as the peel strength [ N/25mm width ] of the decorative sheets obtained in examples and comparative examples, using a Tensilon universal tester "RTC-1250A" (Orientec co., Ltd.) when the transparent resin film was peeled from the substrate on which the pattern layer was laminated at a tensile speed of 200mm/min and a peeling angle of 180 °.

< Presence or absence of air bubbles >

The decorative sheets obtained in examples and comparative examples were evaluated by visual inspection of the printed patterns according to the following criteria. The results are shown in table 1.

++: the printed pattern can be clearly seen

+: the printed pattern appeared slightly discolored (blurred)

-: printed patterns < maximum height roughness > cannot be clearly seen

In the examples and comparative examples, the maximum height roughness (surface maximum height roughness) of the surface having the surface protective layer and the maximum height roughness (bonding surface maximum height roughness) of the surface having the primer layer for bonding were measured by a surface roughness meter (SURFCOM FLEX-50A, trade name, manufactured by tokyo co corporation) in accordance with JIS B0601(2001) in the following evaluation lengths: 12.5mm, measurement speed: 0.6mm/s, cut-off value: 2.5mm, filter type: gaussian, shape removal: straight line, λ s value: 8.0 μm. The results are shown in table 1.

< touch feeling >

The decorative sheets obtained in examples and comparative examples were evaluated for hand touch feeling by using 10 adult men and women as testers according to the following criteria. The results are shown in table 1.

++: the number of testers evaluating good hand feeling was 9 or more

+: the number of testers evaluating good hand feeling was 6 or more

-: the number of testers evaluating the hand feeling was less than 6 [ < design visibility ]

The decorative sheets obtained in examples and comparative examples were visually observed and evaluated according to the following criteria. The results are shown in table 1.

++: the printed pattern formed by the pattern layer can be clearly seen.

+: the printed pattern formed by the pattern layer appeared to be slightly discolored (blurred).

-: the printed pattern formed by the pattern layer cannot be clearly seen.

[ Table 1]

Industrial applicability of the invention

The present invention provides a transparent resin film which can impart excellent design properties to a decorative sheet and has excellent adhesion properties. The decorative sheet of the present invention has excellent design properties and excellent adhesion properties, and is therefore suitable for use in floor boards for housing, doors such as door and window partitions and sliding doors.

Description of the symbols

10: a transparent resin film; 12: a primer layer for adhesion; 13: a surface protection layer; 14: a thermoplastic resin layer; 20: a decorative plate; 23: an adhesive layer; 24: a pattern layer; 25: a substrate.