JP2003118050A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To certainly improve the scratch resistance of a decorative sheet having a surface protection layer. SOLUTION: In the decorative sheet constituted by laminating an uppermost surface A-layer 1 comprising a curable layer on a B-layer 2 comprising a single layer or a multilayer as the surface protection layer, the B-layer has a ethylene/ styrene copolymer resin layer. Further, if a decorative layer 4 or an uneven pattern and decorative treatment by printing or embossing are applied to either one of the layers constituting the decorative sheet, design effect is enhanced. Furthermore, an adhesive layer 5 is appropriately provided between the layers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet which can be used for surface makeup of building exteriors, interiors, fittings, furniture, vehicle interiors and the like.

[0002]

2. Description of the Related Art In a conventional decorative sheet, a vinyl chloride resin sheet has been frequently used as a resin sheet for a base sheet and the like. However, recently, from an environmental standpoint, etc., a resin sheet of a polyolefin resin such as polypropylene or an olefin thermoplastic elastomer has been used as a non-vinyl chloride resin sheet instead of the resin sheet (special feature: JP-A-54-62255, JP-A-6-210
808, JP-A-11-221888, etc.).

[0003]

However, if the surface of the decorative sheet is a resin sheet made of, for example, a polyolefin resin, scratch resistance may be insufficient. The scratch resistance tends to be improved by coating a curable resin layer such as urethane resin on the surface, but the scratch resistance may not be improved by simply providing the curable resin layer.

That is, an object of the present invention is to surely obtain scratch resistance in a decorative sheet having a hard resin layer as the outermost surface layer.

[0005]

In order to solve the above problems, therefore, in the decorative sheet of the present invention, the outermost surface layer A made of a curable resin and the layer B composed of a single layer or multiple layers are laminated. In the decorative sheet formed as described above, the layer B has an ethylene-styrene copolymer resin layer. Although such a structure, that is, the problem to be solved is the physical property of the surface called scratch resistance, attention is paid to the B layer below the A layer which is the outermost surface layer, and the ethylene-styrene copolymer is contained in the B layer. Providing a layer made of a polymer resin provides good scratch resistance, probably because the ethylene-styrene copolymer resin has a good deformation recovery property (the property in which the recessed portion returns to its original shape).

The decorative sheet of the present invention has the above-mentioned structure in which any of the layers constituting the decorative sheet is subjected to a decoration treatment such as printing or embossing. With such a configuration, the decorative treatment improves the design.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

Outline : First, the cross-sectional view of FIG. 1 shows some of the form examples of the decorative sheet of the present invention. The decorative sheet S illustrated in FIG. 1A has an outermost surface A made of a curable resin.
B layer 2 composed of multiple layers (4 layers in the figure) under layer 1
Is a laminated sheet, and has an ethylene-styrene copolymer resin layer 3 (hereinafter also simply referred to as “EtSt layer”) as a resin layer immediately below the A layer 1 in the B layer 2. is there. Further, in the figure, the B layer 2 is EtSt.
Below the layer 3, an adhesive layer 5, a decorative layer 4, and a non-EtSt (ethylene-styrene copolymer resin) layer 6 made of a material (resin, paper, metal foil, etc.) other than the ethylene-styrene copolymer resin.
As a constituent layer. In the case of FIG. 1A, the EtSt layer 3 is usually formed as a transparent layer, and the non-EtSt layer 6 is usually formed as an opaque layer (coloring hiding layer). On the other hand, FIG.
The decorative sheet S illustrated in (B) has a configuration in which a non-EtSt layer 6b is further provided between the EtSt layer 3 immediately below the A layer 1 and the adhesive layer 5 in addition to the configuration of FIG. It is a makeup sheet. The non-EtSt layer 6a below the decoration layer 4 and the non-EtSt layer 6b above the decoration layer 4 may be made of the same material or may be made of different materials. 1A and 1B, the EtSt layer 3 is an example immediately below the A layer 1, but the EtSt layer may be located at any position in the B layer 2 [FIG. And FIG. 4].

Each layer will be described in more detail below.

A layer : A layer 1 is a layer made of a curable resin provided as the outermost surface layer of the decorative sheet. The layer A is provided as a layer of a cured product of a curable resin. As a result, the basic performance for obtaining scratch resistance can be obtained. For this basic performance, Et in the B layer below the A layer
By providing the St layer, good scratch resistance can be surely obtained. The A layer is usually provided as a transparent layer so that the decoration layer can be seen through because a decorative layer or the like is usually provided in the B layer, but it may be an opaque layer depending on the design expression.

The thickness of the layer A made of a curable resin is
If it is too thin, the scratch resistance decreases, so the thickness is usually set to about 4 to 20 μm. The formation of such an A layer is usually performed by using a known coating method such as gravure coating or roll coating with a coating liquid containing a curable resin for the B layer, which can secure the shape as a sheet. can do.

[Resin for Layer A] As the curable resin used for the A layer 1, various curable resins such as thermosetting resins and ionizing radiation curable resins can be used. As the curable resin to be used, a known curable resin such as a two-component curable urethane resin, an epoxy resin, an acrylate-based ionizing radiation curable resin or the like may be appropriately adopted depending on the required physical properties. Incidentally, in the layer A, if necessary, calcium carbonate, a matting agent such as silica, a lubricant such as alumina and silica, an ultraviolet absorber, a light stabilizer such as a hindered amine radical scavenger, and the like,
Known additives such as colorants can be added.

The two-component curing type urethane resin is a urethane resin containing a polyol as a main component and a polyisocyanate as a cross-linking agent (curing agent). The polyol is a compound having two or more hydroxyl groups in the molecule. , For example polyethylene glycol, polypropylene glycol,
Acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. Polyisocyanate is a compound having two or more isocyanate groups in the molecule, for example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, or Aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate are used. Alternatively, as the polyisocyanate, an adduct or a multimer of the above-mentioned various polyisocyanates, for example, an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer (tri) is used.
mer) and the like are also used.

By the way, the curable resin may be a thermosetting resin such as a two-component curing type urethane resin. Especially, the ionizing radiation curable resin is more scratch resistant or has other surface physical properties than the thermosetting resin. It is preferable in that the required physical properties such as can be easily improved. Further, the ionizing radiation curable resin has a faster curing speed than the thermosetting resin and has good productivity. Further, among the ionizing radiation curable resins, the electron beam curable type is more preferable than the ultraviolet ray curable type in that instant curing is possible.

The ionizing radiation-curable resin is a composition curable by ionizing radiation, and specifically, a prepolymer having a radically polymerizable unsaturated bond or a cationically polymerizable functional group in the molecule. A composition curable by ionizing radiation (which includes so-called oligomers) and / or a monomer is appropriately used is preferably used. These prepolymers or monomers are used alone or in combination of two or more.

The above-mentioned prepolymer or monomer specifically has a radically polymerizable unsaturated group such as a (meth) acryloyl group and a (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group, etc. in the molecule. Consisting of a compound having. In addition, a polyene / thiol-based prepolymer obtained by combining polyene and polythiol is also preferably used. In addition, for example, a (meth) acryloyl group is
It means an acryloyl group or a methacryloyl group. Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate. Etc. can be used. A molecular weight of about 250 to 100,000 is usually used.

An example of the monomer having a radically polymerizable unsaturated group is a monofunctional monomer such as methyl (meth).
There are acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.
Further, as a polyfunctional monomer, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth)
There are also acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. In addition, as the polyene, there is a polyene in which allyl alcohol is added to both ends of polyurethane made of diol and diisocyanate.

When curing with ultraviolet rays or visible light, a photopolymerization initiator is further added to the above ionizing radiation curable resin. In the case of a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or as a mixture as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. In addition,
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

As the ionizing radiation, an electromagnetic wave or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) is used. Usually used are ultraviolet rays or electron beams, but in addition,
It is also possible to use visible light, X-rays, ion rays and the like.
As the ultraviolet ray source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp is used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is usually mainly used. As the electron beam source, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. are used, preferably 100 to 1000 keV. Is used to irradiate electrons having an energy of 100 to 300 keV.

If necessary, a thermoplastic resin such as polyvinyl acetate, an acrylic resin or a cellulose resin may be added to the ionizing radiation curable resin.

B layer : The B layer 2 is located below the A layer and is composed of a single layer or a multilayer, and in the case of a single layer, the entire B layer, and in the case of a multilayer, at least one of them. Et the layers
It is a layer configured as an St layer. The layer B is not particularly limited to the above and various structures (under the surface protective layer (A layer)) in the conventionally known decorative sheet can be adopted.

[Layer Structure of Layer B] Some specific examples of the layer structure of layer B will be illustrated below. First, as the simplest configuration, in the case of a single B layer without a decoration layer, the EtSt layer is provided as a resin sheet. The makeup sheet is
The resin layer is formed by coating the layer A on the resin sheet. In this case, the resin sheet is usually colored and opaque (or transparent) as a decoration treatment.

The layer structure of the B layer in the case of multiple layers includes a combination of an EtSt layer provided as a resin sheet or the like and a non-EtSt layer made of another resin material, but is typically a decorative layer. Is a configuration including, for example, E
Combination of tSt layer and decorative layer, EtSt layer and non-EtS
There are combinations of the t layer and the decorative layer. Also, EtSt
The layer, the non-EtSt layer, the decorative layer, and the like are appropriately laminated in between with an adhesive layer. These are all constituent layers of layer B.

The EtSt layer and the non-EtSt layer are respectively
It is configured as a transparent layer or a colored layer (opaque layer) or the like. At this time, usually, a decorative layer is often provided on the upper side (A layer side) of the opaque layer and a decorative layer is provided on the lower side of the transparent layer. In the case of having a transparent layer and an opaque layer, the transparent layer is on the upper side of the opaque layer, and a decorative layer is provided between these layers. Further, the transparent layer and the opaque layer each have a single layer or a multilayer structure. Although the colored layer is used herein as an opaque layer, the B layer also includes a colored transparent layer (colored transparent layer).

A specific example of the layer structure is shown in FIG.
In the decorative sheet S illustrated in (A), the B layer 2 has a four-layer structure, the non-EtSt layer 6 made of an opaque resin layer or the like is provided below the EtSt layer 3 that is a transparent layer, and the decorative layer is provided from the lower side. 4 and the adhesive layer 5 were laminated. Also, FIG.
The B layer 2 of the decorative sheet S of (B) has a five-layer structure, and is an EtSt layer 3 and a non-EtSt layer 6b, an adhesive layer 5, a decorative layer 4, and an opaque resin, which are two-layer transparent resin layers in order from the upper side. The non-EtSt layer 6a composed of layers and the like was laminated.

There can be various configurations of the B layer, and more various configuration examples can be found in a part thereof in Table 1-1. Table 1
-1 describes the configuration of the embodiment, in which the non-EtSt layer is also a resin layer, and the notation of the decorative layer and the adhesive layer (and their positional relationship) is omitted. Table 1-1 lists various configurations in which the resin layer of the EtSt layer and the non-EtSt layer is used as the transparent layer or the coloring layer (opaque layer) in the layer B of the multilayer configuration.

It should be noted that the above examples are for understanding the variety of the constitutional examples of the B layer, and the constitution of the B layer is not limited to the constitution described here. Each layer of the B layer is laminated by a known forming method. For example, the EtSt layer is
It is formed on the resin sheet or another layer by a melt extrusion method or the like. The same applies to the resin layer as the non-EtSt layer.
The resin layer such as the EtSt layer is formed by a multi-layer melt extrusion method. When the non-EtSt layer is paper or metal foil, it is of course prepared as a sheet.

[EtSt Layer] The EtSt layer 3 is a layer made of an estin-styrene copolymer resin. When the surface of the decorative sheet is scratched by a pointed object such as a pencil when the surface of the decorative sheet is scratched by the external stress (load), the EtS layer does not absorb the external stress (load) EtS.
After the t layer is dispersed and external stress is released, it is considered that the t layer has a deformation recovery property that restores the depression to the original state. Therefore, it is considered that scratch resistance is improved by providing the EtSt layer on the B layer below the A layer.

In terms of dispersing the external stress, Et is
In addition to the St layer, the olefinic thermoplastic elastomer layer can also obtain the stress dispersion effect, but the degree of stress (load) causing scratches on the surface and the degree of recovery of the dents are different from those of the EtSt layer. Is better. Further, the ethylene-styrene copolymer resin is advantageous in cost over the thermoplastic elastomer because the raw materials are inexpensive monomers of ethylene and styrene.

The position of the EtSt layer in the B layer is directly below the A layer so as to be in contact with the A layer, and the scratch resistance improving effect can be obtained not only in the position not in contact with the A layer. It may be in position. However, when a non-resin layer such as paper or a metal foil is used as the non-EtSt layer, the EtSt layer is usually more than the non-resin layer in order to exhibit the deformation recovery property of the EtSt layer and contribute to the improvement of scratch resistance. Also, it is preferable to set the layer A side.

The ethylene-styrene copolymer resin used for the EtSt layer preferably has a copolymerization ratio of 5 to 40% in terms of mole fraction of styrene. The molar fraction is 40%
If it exceeds, the resin becomes too sticky and difficult to use. On the other hand, when the molar fraction is less than 5%, the characteristics as a copolymer become poor and the physical properties of the ethylene homopolymer do not change. In addition, various known additives such as a colorant, a filler, a foaming agent, a flame retardant, and an antioxidant may be appropriately added to the EtSt layer if necessary.

The EtSt layer may be prepared by itself as a resin sheet, or may be formed by forming a film on another layer of the B layer by a melt extrusion method or the like.
The thickness of the layer needs to be a certain thickness or more in order to disperse and relax the external stress. Therefore, the thickness of the EtSt layer depends on the material of the intervening layer between the A layer and the EtSt layer, etc.
Usually, it should be 10 μm or more. Considering the case of using it as a base material sheet having a function of retaining the shape of the decorative sheet, the thickness is usually about 30 to 300 μm.

[Non-EtSt Layer] The non-EtSt layer 6 is a layer other than the decorative layer and the adhesive layer, and is a layer made of a material other than the ethylene-styrene copolymer resin. As the non-EtSt layer,
A resin layer is typical, but there are also layers made of paper, metal foil, or the like. Usually, paper or metal foil is used as a base sheet having a shape retaining function, but a resin layer can also be used as a base sheet (resin sheet).

A thermoplastic resin is usually used as the resin. As the thermoplastic resin, a vinyl chloride resin may be used, but from the viewpoint of environmental protection, a resin containing no halogen such as chlorine is preferable. For example, a polyolefin resin, an ABS resin (acrylonitrile-butadiene-styrene copolymer). , A copolyester resin, an acrylic resin, a cellulosic resin, etc. are used. In addition, various known additives such as a colorant, a filler, a foaming agent, a flame retardant, and an antioxidant are appropriately added to the resin layer as necessary. As the colorant, a known colorant, for example, those listed below in the decorative layer can be used.

As the above-mentioned polyolefin resin, polyethylene (PE), polypropylene (PP),
Ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, polymethylpentene, olefin-based thermoplastic elastomer, ionomer and the like are used. Further, as the copolymerized polyester resin, an ethylene-isophthalate-terephthalate copolymer, a polyester-based thermoplastic elastomer (a highly crystalline and high-melting aromatic polyester in the hard segment, a glass transition temperature of -70 ° C in the soft segment) A block polymer or the like using the following non-crystalline polyether etc., for example, polybutylene terephthalate is used for the highly crystalline and high melting point aromatic polyester, and the non-crystalline polyether is Methylene glycol or the like is used), completely amorphous polyester (typically, ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer) is used.

The non-EtSt layer paper includes thin paper, kraft paper, titanium paper, fine paper, coated paper, and the like, and the metal of the metal foil includes aluminum, copper, stellenless, iron, and the like.

[Adhesive Layer] Improvement of adhesion between the B layer and the A layer, or improvement of adhesion between layers such as a decorative layer and a resin layer when the B layer has a multi-layered structure, or a decorative sheet and an adherend. When it is necessary to improve the adhesiveness, etc., it is preferable to perform an easy adhesion treatment. As the easy adhesion treatment, corona discharge treatment, plasma treatment, adhesive layer (also referred to as primer layer or anchor layer)
Known processes such as formation are appropriately performed. The adhesive layer is also used as an adhesive when laminating resin sheets together by a dry lamination method or the like. As these adhesive layers, those suitable for the material to be adhered may be appropriately used. For example, a curable resin such as a thermosetting resin or a resin such as a thermoplastic resin is used. Specific examples of the resin include
For example, two-component curing type urethane resin, polyester resin,
Acrylic resin or the like is used alone or as a mixture. The adhesive layer can be formed by a known coating method such as gravure coating or roll coating.

To show an example of use of the adhesive layer, in the decorative sheet S illustrated in FIGS. 1A and 1B, EtSt in the B layer 2 is used.
An adhesive layer 5 is provided between the layer 3 and the decorative layer 4. Further, in the decorative sheet S illustrated in FIG. 3, the adhesive layer 5a is provided between the EtSt layer 3 and the decorative layer 4, and the lower non-EtSt layer is provided.
An adhesive layer 5b is provided on the back surface side of the layer 6a, and an adhesive layer 5c is provided as a layer in contact with the A layer 1 on the outermost surface side of the B layer 2.
Of course, the adhesive layer can be omitted if unnecessary.

[Decoration Treatment] A decorative sheet having a higher design can be obtained by applying a decoration treatment such as printing or embossing to any of the layers constituting the decorative sheet. Specifically, any of the above layers is, for example, an EtSt layer or a non-EtSt layer that constitutes the B layer, or an A layer. As a typical example of decoration processing,
(1) Addition of a colorant into the resin layer (colored transparent or colored opaque), (2) Formation of the decorative layer 4 by printing or the like expressing a pattern or the like [see FIGS. 1 (A) and (B)], embossing The shape of the concavo-convex pattern 8 (see FIG. 2) and the like can be cited.
For such decoration treatment, various conventionally known decoration treatments for general decorative sheets can be appropriately adopted. In addition, these various decoration treatments may be used in appropriate combination depending on the application.

(1) Addition of coloring to the resin layer: An example of adding coloring to the resin layer is typically coloring of the opaque resin layer of the B layer. In addition, the resin layer, which is a transparent layer of the B layer, may be colored to make it transparent or colored, or may be colored to make the A layer transparent. As the colorant, a known colorant, for example, those listed below in the decorative layer can be used.

(2) Formation of decorative layer: The decorative layer 4 is a constituent layer of the B layer 2, and the formation thereof is on either side of the EtSt layer or the non-EtSt layer which can be a base sheet having a shape retaining function. Do against. The forming surface depends on the application, the laminating method and the like. The decorative layer 4 is formed as a pattern printing layer, a metal thin film layer, or the like in order to add a pattern or the like. The surface on which the decorative layer is formed is preferably the outermost surface of the decorative sheet, the inside avoiding the outermost surface, for example, the outermost surface side of the B layer or the B layer so that the decorative sheet can be protected from both front and back surfaces against scratches and the like. In the case of a multi-layer structure, the surface between the layers is good (see FIG. 1).

The pattern printing layer can be formed by a known printing method such as gravure printing, silk screen printing, offset printing, letterpress printing, flexographic printing, electrostatic printing, ink jet printing, transfer printing and the like. When the pattern of the decorative layer is entirely solid, it can be formed by a known coating method such as roll coating.

The pattern of the decorative layer is, for example, a wood grain pattern, a stone grain pattern, a sand grain pattern, a tile pasting pattern, a brickwork pattern,
It is a textured pattern, a leather pattern, a geometrical figure, a character, a symbol, various abstract patterns, or a solid pattern, or a combination thereof.

As the ink (or paint, the same applies hereinafter) used for the pattern printing layer, known ones can be used. For example, as the binder resin of the ink, chlorinated polyethylene such as chlorinated polyethylene and chlorinated polypropylene, polyester resin, thermoplastic urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, cellulose resin A curable resin such as a thermoplastic resin such as a two-component curing type polyurethane resin, a polyester resin, an epoxy resin, or an ionizing radiation curable resin that is cured by ionizing radiation such as ultraviolet rays or electron beams can be used. . Further, as the colorant of the ink, inorganic pigments such as titanium white, carbon black, rouge, yellow lead, ultramarine blue, organic pigments such as aniline black, quinacridone, isoindolinone, phthalocyanine blue, and titanium dioxide-coated mica foil powder. And other bright pigments, or other dyes are used.

The metal thin film layer as the decoration layer is formed by using a metal such as aluminum, chromium, gold, silver and copper by a method such as vacuum deposition and sputtering. The metal thin film layer is partially provided in a pattern or over the entire surface.

(3) Impression of uneven pattern: The uneven pattern 8 is shaped by hairline processing, sandblasting, embossing, or the like. For example, the embossing is performed by pressing the embossing plate against the surface of the heat-softened resin layer by using a hot-press type sheet-fed or rotary embossing machine. As the uneven pattern, there are wood grain board conduit grooves, stone plate surface unevenness (granite cleavage surface, etc.), tiled or brick-laid joint grooves, cloth surface texture, satin, sand, hairline, line-shaped groove and the like. The uneven pattern may be a combination of these. The surface on which the uneven pattern is formed is usually the surface of the A layer, and may be directly formed on the surface of the A layer. However, after forming on the outermost surface of the B layer, the A layer is formed to form A. It is also possible to give an uneven pattern to the surface of the layer. In addition, the uneven pattern may be provided between the layers in the B layer having a multi-layered structure or on the surface which is the back side surface of the B layer. Further, the uneven pattern can be formed simultaneously with the film formation by using an embossing / cooling roller having an uneven pattern on the cooling surface as a cooling roller when forming the resin sheet. Further, similarly to this, for example, in the case of a B layer having a multi-layered structure, when the resin layer is laminated simultaneously with the film formation, the resin layer can be shaped on the surface of the resin layer.

Adherend : As an adherend to which the decorative sheet is attached, an adherend suitable for the intended use is used. Specific examples of the adherend include flat plates made of various materials, plate materials such as curved plates, three-dimensional shaped articles, sheets (or films), and the like. For example, wood veneer, wood plywood, particle board, wood fiber board or other wood fiber board, MDF (medium density fiber board), etc., wood board material used as a three-dimensional article, iron, aluminum, etc. board, three-dimensional article or Ceramics such as metal materials used as sheets, glass, ceramics such as ceramics, non-cement ceramics materials such as plaster, non-ceramic ceramics materials such as ALC (lightweight aerated concrete) plates, ceramics used as three-dimensional shaped articles, etc. -Based material, polyolefin resin such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, plate material such as rubber, three-dimensional shape A resin material used as an article or sheet, or exclusively a sheet High-quality paper to be used as,
Paper such as Japanese paper, carbon, asbestos, glass, non-woven fabric or woven fabric made of fibers such as synthetic resin, or a material that is a composite of two or more of these materials, for example, wood powder used as a plate or a three-dimensional shaped article. Plastic, paper powder plastic,
Alternatively, a composite (base) material such as FRP (fiber reinforced plastic), which is typified by reinforcing an unsaturated polyester resin with a fiber such as glass fiber, or a combination thereof can be used.

Application of decorative sheet: The application of the decorative sheet of the present invention is not particularly limited. For example, interior materials for buildings such as walls, floors and ceilings, exterior materials for buildings such as outer walls, roofs, door exteriors, window frames, surface materials for furniture such as chests, shelves, desks, and rims,
Base materials such as skirting boards, door frames, cabinets for electric devices such as television sets, surface materials for home appliances such as refrigerator doors, interior materials for vehicles such as automobiles, trains and ships.

[0049]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1] A decorative sheet S having a cross-sectional view of Fig. 3 was produced as follows. First, as the non-EtSt layer 6a which becomes a colored layer (opaque resin layer) in a part of the B layer 2,
A polyethylene resin film with a thickness of 60 μm and made opaque brown by adding a colorant (manufactured by Okura Industry Co., Ltd., trade name “E
-5 "), corona discharge treatment was applied to both sides of this resin film to obtain a wetting index of 45 mN / m (45 dyn / c).
m), and then on the surface to be the front side, by a gravure printing method, a decorative layer 4 having a wood grain pattern with a urethane resin-based ink,
As the easy-adhesion treatment, the adhesive layer 5a on the entire surface was sequentially formed with a polyester adhesive. Next, on the back surface of this resin film, as an easy-adhesion treatment, an entire adhesive layer 5b made of urethane resin-based ink was formed by a gravure printing method to prepare a printing sheet.

Next, as a transparent layer (transparent resin layer) having a two-layer structure, which is a part of the B layer 2, a polypropylene resin (manufactured by Sun Allomer Co., Ltd., “Sun Allomer (registered trademark) PM”) is used.
600A ") and an ethylene-styrene copolymer resin having a styrene content of 25 mol% by a melt (multilayer) extrusion coating method using a T-die with a thickness ratio of 1: 1 (polypropylene: EtSt). Simultaneously with the film formation, EtS is applied to the decorative layer forming surface side of the printing sheet so that the total thickness becomes 80 μm.
The layers were laminated so that the t layers 3 were in contact with each other to obtain a laminated sheet. In the transparent layer having a two-layer structure, the decorative layer 4 side is the EtSt layer 3 and the A layer side is the non-EtSt layer 6b made of polypropylene resin.

Next, the non-EtSt layer 6b of the above laminated sheet.
After the uneven pattern 8 of the wood grain conduit groove was formed on the surface of No. 1 by hot embossing, corona discharge treatment was applied to the formed surface to obtain a wetting index of 45 mN / m, and then the urethane primer agent was applied by the gravure coating method. Adhesive layer 5c with a thickness of 2 μm
And electron beam curable ink (manufactured by Dainichiseika Kogyo Co., Ltd., trade name "EBF-700", universal hardness 140N /
mm ² ) crosslinked and cured to form a transparent A layer 1 having a thickness of 15 μm
And were formed on the entire surface to obtain a desired decorative sheet S as shown in the sectional view of FIG.

Then, the above decorative sheet S is prepared by using a urethane resin-based two-component curing type adhesive to make a MDF having a thickness of 2.5 mm.
The laminate was laminated on (medium-quality fiberboard) and the adhesive was cured to produce a decorative board, and the performance of the decorative board was evaluated. The results are summarized in Table 1-1.

Example 2 A decorative sheet S having a cross-sectional view shown in FIG. 4 was produced as follows. First, as the non-EtSt layer 6 which is a transparent layer in a part of the B layer 2, a transparent polypropylene resin film having a thickness of 120 μm (trade name “PC301S” manufactured by Mitsubishi Chemical MKV Co., Ltd.) is used. After the corona discharge treatment was applied to the back side surface to obtain a wetting index of 45 mN / m (45 dyn / cm), a pattern pattern layer and a colored concealing solid layer were formed by a gravure printing method using a urethane resin-based ink as a decorative layer 4 for a wood grain pattern. The layers were sequentially formed to produce a printed sheet.

Next, an ethylene-styrene copolymer resin having a styrene content of 25 mol% was used as a transparent layer on the non-printing side, which was the front side of the above-mentioned printing sheet, by a melt extrusion coating method using a T-die. , Applied at the same time as the film formation, thickness 80
A laminated sheet in which a transparent EtSt layer 3 of μm was laminated was obtained.

Thereafter, the uneven pattern 8, the adhesive layer 5c, and the A layer 1 were sequentially formed in the same manner as in Example 1 to obtain a desired decorative sheet S as shown in the sectional view of FIG. Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Example 3] In Example 1, instead of forming two transparent layers by a melt extrusion coating method on the decorative layer forming surface side of the printing sheet, the following three transparent layers were formed. did. In the three transparent layers, an intermediate layer is an EtSt layer having a thickness of 35 μm (resin is the same as that in Example 1), and the upper side is a polypropylene resin (manufactured by Sun Allomer Co., Ltd., “Sun Allomer (registered trademark) PM600A”) having a thickness of 35 μm. Non-EtS
Adhesive polypropylene-based resin (made by Mitsubishi Chemical Corporation, "MODIC (registered trademark) -AP P-"
517 ″) and a non-EtSt layer having a thickness of 10 μm. Otherwise, a decorative sheet was produced in the same manner as in Example 1 (see Table 1-1). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

Example 4 Instead of forming two transparent layers on the decorative layer side of the printing sheet by the melt extrusion coating method in Example 1, a single transparent layer having a thickness of 80 μm Et is used.
A decorative sheet was produced in the same manner as in Example 1 except that the St layer 3 (resin is the same as in Example 1) was formed. Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1,
The performance was evaluated.

[Example 5] In Example 1, the coloring layer was colored under the non-EtSt layer 6a, which was a coloring layer (opaque resin layer) of polyethylene resin, with a thickness of 40 µm by coloring. Opaque EtSt layer (resin of Example 1
Same as the above), and EtSt is used for the transparent layer.
No layer was provided, and the following two transparent layers were formed. The upper side of the two transparent layers is a polypropylene-based resin ("Sun Allomer (registered trademark) PM600" manufactured by Sun Allomer Co., Ltd.).
A)), a non-EtSt layer having a thickness of 72 μm, and the lower side is an adhesive polypropylene resin (manufactured by Mitsubishi Chemical Corporation,
A non-EtSt layer having a thickness of 8 μm and made of “MODIC (registered trademark) -APP-517”). Otherwise, a decorative sheet was produced in the same manner as in Example 1 (see Table 1-1). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Embodiment 6] In Embodiment 5, except that the EtSt layer in the colored layer of layer B is changed from the lower side to the upper side,
A decorative sheet was prepared in the same manner as in Example 5 (Table 1-1).
reference). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Embodiment 7] In Embodiment 2, except that the EtSt layer in the transparent layer of layer B is changed from the upper side to the lower side,
A decorative sheet was produced in the same manner as in Example 2 (Table 1-1)
reference). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Embodiment 8] In the first embodiment, the ink used for forming the layer A is changed from the electron beam curable ink to the two-component curable urethane resin ink, and cross-linked and cured to form the layer A. A decorative sheet was produced in the same manner as in Example 1 except for the above (see Table 1-1). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Comparative Example 1] In Example 3, the middle is E
Instead of providing three transparent layers as tSt layers, the Et
The St layer was omitted, and two transparent layers were formed. However, the total thickness of the formed transparent layer was kept at 80 μm, the upper non-EtSt layer made of polypropylene resin was 72 μm, and the lower non-EtSt layer made of adhesive polypropylene resin was 8 μm. Other than the above, a decorative sheet was produced in the same manner as in Example 1 (see Table 1-2). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Comparative Example 2] In Example 1, when forming the two transparent layers, a soft polypropylene resin (trade name "Cataloy KS359P" manufactured by Sun Allomer Co., Ltd.) was used instead of the lower EtSt layer. ) Consisting of 40 μm
A decorative sheet was produced in the same manner as in Example 1 except that the non-EtSt layer was prepared (see Table 1-2). Further, using this decorative sheet, a decorative plate was prepared in the same manner as in Example 1 and its performance was evaluated.

[Performance Evaluation Results] Scratch resistance was evaluated by a Hoffman scratch tester (BYK-Gar, USA).
dner company make, load 7.85N (800g
The presence or absence of scratches on the surface of the A layer during the test in f) was observed, and it was evaluated as good without scratches and poor with scratches.
The test was conducted with a scratch blade (edge part of a cylinder with a diameter of 7 mm) so that it contacts the surface of the test piece at an angle of 45 degrees.
Set, move the scratch blade like pulling,
Rub the surface. At that time, the load applied to the scratch blade is changed to read the load when scratches occur on the surface of the test body. The Hoffman scratch test is based on the Naval Research Laboratories standard (Naval Research Laboratories).
atory (NRL) Specification)
However, it is said that it is closer to the scratching when an object is actually dragged than the pencil hardness test (pencil scratch value) of JIS K 5400.

The results are shown in Tables 1-1 and 1-2. Examples 1 to 8 in which the EtSt layer was provided in the B layer.
In each case, the scratch resistance was good regardless of the position of the EtSt layer in the B layer. On the other hand, in Comparative Examples 1 and 2 in which the EtSt layer was not provided in the B layer at all, scratch resistance was poor.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

(1) According to the decorative sheet of the present invention, scratch resistance is improved. (2) Further, if the structure is subjected to decoration processing such as printing and embossing, the designability is improved.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating two forms of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view illustrating another form of the decorative sheet of the present invention.

FIG. 3 is a cross-sectional view illustrating another form of the decorative sheet of the present invention.

FIG. 4 is a cross-sectional view illustrating another form of the decorative sheet of the present invention.

[Explanation of symbols]

1 A layer 2 B layer 3 EtSt layer 4 decorative layers 5 Adhesive layer 5a, 5b, 5c adhesive layer 6 Non-EtSt layer 6a, 6b, 6c Non-EtSt layer 8 uneven pattern S makeup sheet

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiko Yasutake             1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo             Dai Nippon Printing Co., Ltd. F term (reference) 4F100 AK01A AK04 AK04B AK07                       AK12B AL01B BA02 BA07                       BA10A BA10B BA15 EH20                       EH23 EJ55 GB08 GB33 HB00                       HB21A HB21B HB31A HB31B                       JB12A

Claims (2)

[Claims] 1. A decorative sheet obtained by laminating an outermost surface A layer made of a curable resin and a B layer composed of a single layer or multiple layers, wherein the B layer has an ethylene-styrene copolymer resin layer. , Makeup sheet. 2. The decorative sheet according to claim 1, wherein any of the layers constituting the decorative sheet is subjected to a decoration treatment such as printing or embossing.