JP2001138469A - Decorative material with hardwearing properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance hardwearing properties without giving rise to a feel of surface roughness and make a sophisticated design representable. SOLUTION: The decorative material D comprises a recoatable ionizing radiation-curable resin layer 3 formed on a base 1 and a transparent resin layer 4 formed on the top surface, and the recoatable ionizing radiation-curable resin layer 3 contains a filler 5. For the transparent resin layer 4, an ionizing radiation-curable resin or a heat-curable resin is used. A pictorial pattern layer 2 or the like is routinely formed between the base 1 and the recoatable ionizing radiation-curable resin layer 3. The unformed part of the transparent resin layer 4A having the unformed part is harmonized with the pictorial pattern of the pictorial pattern layer 2. In addition, the transparent resin layer 4A may be formed on a matted layer 6 and thereby a feel of design and a surface texture due to a luster difference pattern are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material used as a decorative paper for surface decoration of a house interior or furniture. In particular, the present invention relates to a decorative material having durable physical properties (abrasion resistance and stain resistance) that can be used on a horizontal surface of furniture and the like.

[0002]

2. Description of the Related Art Conventionally, among the decorative materials used for, for example, building interiors and fittings, the outermost transparent resin layer serving as a top coat layer has a thermosetting two-component curing material made of urethane resin or the like. Curing resin such as a mold resin, or an ionizing radiation curable resin that is cured by ionizing radiation such as ultraviolet rays or electron beams,
It is used from the point of abrasion resistance and stain resistance. Particularly, in order to further improve the wear resistance and the surface hardness, a filler is often added to the transparent resin layer. For example, in Japanese Patent No. 2740943 (JP-A-8-183147), after a picture layer is formed on a substrate, a wear-resistant resin layer containing a filler in a crosslinkable resin as the outermost surface layer is formed thereon. A makeup material having a provided configuration is disclosed. In Japanese Patent Application Laid-Open No. 10-119226, a pattern layer is formed on a substrate, a heat-drying ionizing radiation-curable resin layer for an intermediate layer is formed on the pattern layer, and a top coat is formed as the outermost layer. A decorative material is disclosed in which an ionizing radiation-curable resin layer for a layer is formed, and a filler is contained in the heat-drying ionizing radiation-curable resin layer for an intermediate layer.

[0003]

However, as described in Japanese Patent No. 2740943, when a filler to be contained in a layer to be the outermost surface layer, sufficient physical properties such as abrasion resistance which can be used on a horizontal surface can be imparted. However, on the other hand, the filler reduces the gloss of the surface due to the filler, and the filler cleaves out on the surface, causing a feeling of surface roughness. If this is actually used for interior use (horizontal surface), it may damage the contacted parts, There was a problem of causing wear. On the other hand, as described in JP-A-10-119226, the filler is not contained in the outermost surface layer but is contained in an inner layer (a heat-drying ionizing radiation-curable resin layer for an intermediate layer). In the case where the top coat layer was provided, the surface was smooth, but only poor design and surface texture were obtained.

[0004] Therefore, an object of the present invention is to provide a decorative material having abrasion resistance capable of expressing a sense of design and surface texture.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, a wear-resistant decorative material according to the present invention comprises:
Having a recoatable ionizing radiation-curable resin layer, having a transparent resin layer on the outermost surface on the recoatable ionizing radiation-curable resin layer, the recoatable ionizing radiation-curable resin layer was configured to contain a filler. . As described above, since the filler is contained in the ionizing radiation-curable resin layer of the inner layer, and the resin layer is recoatable, a transparent resin layer or the like is formed on the resin layer while the resin layer remains uncured. After the resin layer is cured and completed without any trouble such as curing the resin layer after forming, a transparent resin layer or the like can be easily formed on the resin layer without a problem of adhesion. In addition, a cosmetic material having a high degree of freedom can be obtained, and it is a wear material having abrasion resistance and easily expressing a sense of design and surface texture. Moreover, the filler is not contained in the outermost transparent resin layer, but in the ionizing radiation-curable resin layer, which is the inner layer. Excellent abrasion resistance can be obtained without causing a problem of surface roughness or damage or abrasion of a surface contact in interior use (horizontal surface).

Further, in the abrasion-resistant decorative material of the present invention, the transparent resin layer is made of an ionizing radiation-curable resin. As described above, by using the ionizing radiation curable resin for the transparent resin layer as the outermost surface, extremely excellent wear resistance can be obtained.

Further, in the wear-resistant decorative material of the present invention, the transparent resin layer is made of a thermosetting resin. As described above, by using a thermosetting resin for the transparent resin layer as the outermost surface, excellent wear resistance can be obtained inexpensively and simply.

The abrasion-resistant decorative material of the present invention has a structure in which any one of the above-described decorative materials has a pattern layer between the substrate and the recoatable ionizing radiation-curable resin layer. As a result, the design layer is further enhanced by the design layer, and by providing the design layer below the recoatable ionizing radiation-curable resin layer, the design layer is protected by the recoatable ionizing radiation-curable resin, and as a result, The wear resistance is extremely excellent.

Further, in the decorative material having wear resistance according to the present invention, in the above decorative material, the transparent resin layer is formed such that an unformed portion thereof is synchronized with the pattern of the pattern layer. For example, the picture layer has a wood grain pattern, and the unformed portion of the transparent resin layer has a wood grain pipe pattern. By forming a transparent resin layer having an unformed portion synchronized with such a pattern layer, a feeling of unevenness due to the presence or absence of the transparent resin layer and a better sense of design and surface texture can be expressed by a sense of synchronization with the pattern layer. it can.

The abrasion-resistant decorative material of the present invention may be such that in the above decorative material, the decorative material is formed closer to the substrate than the transparent resin layer having an unformed portion, and is exposed at least in the unformed portion. And a matte layer formed on the recoatable ionizing radiation-curable resin layer. In this way, a matte layer is provided between the transparent resin layer and the recoating ionizing radiation-curable resin layer to expose the matte layer at a portion where the transparent resin layer is not formed. The pattern due to the difference in the degree of surface gloss of both layers provides a decorative material with further improved design and surface texture.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a wear-resistant decorative material according to the present invention will be described with reference to the drawings.

First, FIG. 1 (A) shows a decorative material D having an abrasion resistance according to the present invention, on which a decorative layer 2 composed of a whole solid layer 2A and a pattern pattern layer 2B is formed on a substrate 1. The ionizing radiation-curable resin layer 3 having a recoating property and the transparent resin layer 4 are formed in this order, and the filler 5 is contained in the ionizing radiation-curable resin layer 3. The decorative layer 2 can be omitted, but usually the
As shown in (A), it is often provided below the ionizing radiation-curable resin layer 3. The transparent resin layer 4 may be made of a thermoplastic resin, but is preferably made of an ionizing radiation-curable resin or a thermosetting resin.

Hereinafter, each layer will be described in detail.

[Base] The shape, material, other characteristics, etc. of the base 1 are not particularly limited. For example, the shape may be a sheet, a plate, a three-dimensional object, or the like. The material is paper, wood, metal, inorganic non-metal (ceramic, non-ceramic ceramics, etc.), resin or the like. Further, any of those having ink permeability (paper, nonwoven fabric, etc.) and those having no ink permeability (resin sheet, etc.) may be used. Above all, paper and resin sheets (films) are typical. If these are used as a substrate, the decorative material of the present invention can be a decorative sheet.

The fibrous substrates other than paper-based materials include polyester resin, acrylic resin, nylon, vinylon,
A nonwoven fabric made of fibers such as glass is also used. As in the case of the paper-based nonwoven fabric, a resin such as an acrylic resin, a styrene-butadiene rubber, a melamine resin, or a urethane resin may be added (the resin is impregnated after paper-making or filled during paper-making).

Examples of the resin system include polyolefin resins such as polyethylene, polypropylene and olefin thermoplastic elastomers, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol and ethylene-vinyl alcohol copolymer, and polyethylene terephthalate. , Polyester resins such as polybutylene terephthalate, acrylic resins such as polymethyl methacrylate, polymethyl acrylate, and polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), cellulose triacetate, cellophane, and polycarbonate And other resin materials such as resin. These resins are used as sheets, plates, and three-dimensional objects. In the resin system, phenolic resin, urea resin, unsaturated polyester resin, urethane resin, epoxy resin, thermosetting resin plate made of thermosetting resin such as melamine resin, phenol resin, urea resin, unsaturated polyester resin, A so-called FRP made by impregnating and curing a resin such as urethane resin, epoxy resin, melamine resin, diallyl phthalate resin into glass fiber nonwoven fabric, fabric, paper, and other various fibrous substrates.
There is also a resin plate such as a (fiber reinforced plastic) plate.

In the wood system, for example, cedar, cypress, oak,
There are wood materials such as veneer, plywood, particle board, fiber board, and glued wood made of lauan, teak and the like. Wood is used as sheets, boards and three-dimensional objects. Further, in the metal system, for example, there are metal materials such as iron, aluminum, stainless steel, and copper. Metals are used as sheets (foil), plates, and three-dimensional objects. In the case of inorganic nonmetals, for example, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete),
There are non-ceramic ceramic materials such as pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, and gypsum slag, and ceramic materials such as earthenware, pottery, porcelain, setware, glass, and enamel. Inorganic nonmetals are mainly used as plates and three-dimensional objects.

Alternatively, a substrate obtained by laminating two or more of the above-mentioned various materials by a known means such as an adhesive or heat fusion to form a composite may be used. For example, resin-impregnated paper, FRP and the like are also examples.

The other characteristics include, for example, the presence or absence of permeation. For example, a substrate without ink permeability is
Vinyl chloride resin, polyethylene terephthalate (PE
T), a resin sheet or the like made of a polyolefin-based resin or the like, and the substrate having ink permeability is, for example, pure white paper for printing,
Papers such as inter-sheet reinforced paper, impregnated paper impregnated with curable resin,
Other fibrous substrates such as woven and nonwoven fabrics.

Although the thickness of the substrate depends on the shape, material, application, etc., for example, when a fibrous substrate such as paper is used,
About 50 to 150 g / m ^{2 in} basis weight and 50 to 30 in thickness
About 0 μm is desirable.

[Recoatable ionizing radiation-curable resin layer] The recoatable ionizing radiation-curable resin layer 3 is a layer containing a filler in the layer and made of an ionizing radiation-curable resin having recoatability (suitability for post-coating). It is. In the present invention, the recoatable ionizing radiation-curable resin layer can be laminated with good adhesion even after being completely cured before forming another layer on the layer. Therefore, the recoatable ionizing radiation-curable resin layer is maintained in a state before complete curing such as uncured or semi-cured, and a transparent resin layer is formed on the layer without adhesion by printing, coating or the like. Can be laminated. On the other hand, when a transparent resin layer or the like is formed on the recoatable ionizing radiation-curable resin in a state before complete curing, and thereafter, when the recoatable ionizing radiation-curable resin layer is completely cured, When forming the transparent resin layer and the like, the recoatable ionizing radiation-curable resin layer must be in a non-adhesive state before the transparent resin layer can be formed by a printing machine or a coating machine. However, if the recoatable ionizing radiation-curable resin layer can be formed on the transparent resin layer with good adhesion even after complete curing, the recoatable ionizing radiation-curable resin layer is in a liquid state even in an adhesive state before complete curing. The ionizing radiation-curable resin can be freely selected according to required physical properties and the like.

In the present invention, the term "recoat property" means
On this (recoatable) ionizing radiation-curable resin layer, a transparent resin layer made of a urethane-based resin, an ionizing radiation-curable resin, a melamine alkyd resin, another resin, or the like was laminated as a coating film with an ink or a coating liquid. In this case, it means that sufficient adhesiveness for practical use is maintained. Specifically, for example, an adhesion test specified in JIS K 5400 (after removing silicone and dirt on the surface of the coated film after recoating with an eraser, use a cutter knife to cut at least the recoating ionizing radiation-curable resin layer. Of the recoatable ionizing radiation-curable resin layer and a layer of a transparent resin layer or the like formed on the recoatable ionizing radiation-curable resin layer by a method in which the cellophane adhesive tape attached to the surface is peeled off and the coating film is peeled off and evaluated based on the peeling state of the coating film. It means that these layers have an adhesion strength such that they do not peel off from each other. The transparent resin layer and the like are usually formed by a coating method, but can be formed not only by the coating method but also by a printing method. Therefore, “recoating”, that is, re-coating (or re-coating) encompasses not only a coating method but also a meaning for lamination by another method such as printing.

The ionizing radiation-curable resin used in the recoatable ionizing radiation-curable resin layer has a radical polymerizable unsaturated bond such as an acryloyl group or a cationic polymerizable functional group such as an epoxy group in the molecule. And a composition comprising a prepolymer (including so-called oligomers) and / or a monomer, which can be cured by ionizing radiation such as ultraviolet rays or electron beams. The prepolymer and the monomer are used alone or as a mixture of two or more. Here, the term “ionizing radiation” means an electromagnetic wave or a charged particle having energy capable of polymerizing or crosslinking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used.

Usually, unsaturated polyesters, polyacrylates, cationically polymerizable epoxies and the like are used as the prepolymer, and styrene, acrylate and unsaturated carboxylic amides are used as the monomers. You.

For example, examples of the prepolymer having a radical polymerizable unsaturated group in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. ) Acrylate, silicone (meth) acrylate and the like can be used. (Meta)
Acrylate means methacrylate or acrylate. Examples of the prepolymer having a cationically polymerizable functional group in its molecule include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. There is.

Examples of monomers having a radical polymerizable unsaturated group in the molecule include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. . In addition, among polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate.

In order to impart a recoating property to a layer made of an ionizing radiation-curable resin to obtain a recoatable ionizing radiation-curable resin layer, the average molecular weight between crosslinks of the ionized radiation-curable resin cured product is 200 to 1000. It is preferable that the design is made so that As means for controlling the average molecular weight between crosslinks, when increasing the average molecular weight between crosslinks, there are means such as reducing the concentration of the added monomer and reducing the number of functional groups of the prepolymer or acrylate monomer. On the other hand, in order to lower the average molecular weight between crosslinks, conversely, the monomer concentration may be increased, or a trifunctional or higher acrylate monomer may be added. The average molecular weight between crosslinks is the average molecular weight between crosslinks = the total molecular weight / the number of crosslink points, and the total molecular weight is Σ (the number of moles of each component × the molecular weight of each component). Is {[{(the number of functional groups of each component −1) × 2} × the number of moles of each component].

When curing with ultraviolet light or visible light, a photopolymerization initiator is further added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination 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 benzoinsulfonic 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 weight based on 100 parts by weight of the ionizing radiation-curable resin.

The source of ionizing radiation may be an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp,
Light sources such as carbon arc lamps, black light fluorescent lamps, and metal halide lamps are used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used. Further, as the electron beam source, various electron beam accelerators such as a Cockcroft-Walton type, a Van degraft type, a resonance transformer type, an insulating core transformer type, or a linear type, a dynamitron type, a high frequency type, and the like are used. ,
Preferably, one that irradiates electrons having an energy of 100 to 300 keV is used. The irradiation dose of electron beam is
Usually, it is about 2 to 15 Mrad.

By including the filler 5 in the recoating ionizing radiation-curable resin layer, the abrasion resistance is improved. As such a filler, for example, inorganic particles such as α-alumina, silica, silicon carbide and the like, organic particles such as cross-linked acrylic resin beads and the like are added to the composition comprising the above ionizing radiation-curable resin and used. The particle shape and the particle size of the filler are arbitrary, but a spherical shape is preferable from the problem of abrasion of a coating liquid coating apparatus for forming a recoatable ionizing radiation-curable resin layer. The particle size of the filler is an average particle size which is usually 0.3% of the thickness of the recoatable ionizing radiation-curable resin layer.
It is good to make it about 2 times. If it is less than 0.3, it is difficult to obtain sufficient abrasion resistance, and if it exceeds 2, the filler may protrude from the surface of the recoatable ionizing radiation-curable resin layer and fall off. In addition, the printability and coating suitability of the transparent resin layer deteriorate due to surface irregularities. In addition, the content of the filler,
The amount may be appropriately determined depending on required physical properties and the like within a range in which the transparency is not impaired beyond the extent that the lower pattern layer can be seen through the recoating ionizing radiation-curable resin layer.

The ionizing radiation-curable resin comprising the above composition is usually used as a liquid coating liquid at room temperature (room temperature or an appropriately heated coating temperature), such as a roll coat, a flow coat, or the like. Coating is performed by a conventionally known coating method. The thickness of the recoatable ionizing radiation-curable resin layer is not particularly limited as long as it is appropriately determined according to required physical properties such as required abrasion resistance, and is, for example, about 10 to 50 μm.

[Transparent Resin Layer] The transparent resin layer 4 is positioned as the outermost surface layer of the decorative material on the recoatable ionizing radiation-curable resin layer and determines the surface properties of the decorative material. Due to the presence of the transparent resin layer as the outermost surface layer, the recoatable ionizing radiation-curable resin layer is eliminated by the presence of the filler in the layer, even if its surface is roughened, so that the decorative material surface has no surface roughness. Things become possible. In addition, the filler contained for the purpose of improving abrasion resistance is contained in the lower layer of the recoating ionizing radiation-curable resin layer, and need not be contained in this transparent resin layer. The surface roughness that can occur, and the problems caused by damage and abrasion of a contact object when the decorative surface is used in a horizontal surface application can be prevented. In addition, the transparent resin layer as the outermost surface layer allows the surface to be roughened and arbitrarily adjusted in gloss as well as a mere smooth surface, so that a decorative material having a rich design feeling and surface texture can be obtained.

As such a transparent resin layer 4, a general-purpose overcoat agent can be used. In particular, in order to improve the surface performance in terms of abrasion resistance, it is preferable that the overcoat agent uses a curable resin. As the curable resin,
A thermosetting resin, an ionizing radiation curable resin, or the like may be used. The formation of the transparent resin layer (generally called a top coat layer)
It may be formed by a known coating method such as roll coating or a known printing method such as gravure printing. Of course, at the time of partial formation, it is formed by a printing method.

As the thermosetting resin, a two-component curable resin can be used. For example, a two-component curable urethane resin is used. As the two-part curable urethane resin, a polyol such as acrylic polyol, polyester polyol, or polyether polyol is used as a main component, and 2,4-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, or isophorone is used as a crosslinking agent (curing agent). It may be appropriately selected from known urethane resins using polyisocyanates such as diisocyanate. Further, as the ionizing radiation-curable resin, the ionizing radiation-curable resin as described in the recoatable ionizing radiation-curable resin layer described above can be used. However, since the recoating property is not required in the transparent resin layer, it is not necessary to add a filler and select a resin in consideration of the recoating property.

The filler for the purpose of improving abrasion resistance is not indispensable in the transparent resin layer. However, the filler may be contained as long as the surface is not roughened. The filler to be contained is the filler as described in the recoatable ionizing radiation-curable resin layer.

The transparent resin layer may contain a filler in order to obtain a desired surface property, for example, for adjusting gloss. For example, a known matting agent such as silica, calcium carbonate, and barium sulfate may be used. By adjusting the gloss, the transparent resin layer can express an arbitrary gloss between glossy and matte, and a decorative material with a rich design feeling and surface texture can be obtained.

As shown in FIG. 1 (B), the transparent resin layer is formed with the unformed portion as a pattern of a pattern layer 2 described later (specifically, a pattern pattern layer 2B having a pattern pattern in the pattern layer). (Pattern), the pattern can be made higher by the transparent resin layer 4A formed partially so as to be synchronized with the pattern of the transparent resin layer 4A. In addition, in order to form the transparent resin layer so as to have an unformed portion, the transparent resin layer may be formed in synchronization with the pattern of the pattern layer 2 by a known printing method.

As an example of synchronization between the unformed portion of the transparent resin layer and the pattern of the pattern layer, for example, the pattern of the pattern layer is a wood grain pattern, and the pattern of the unformed portion is a pattern synchronized with the annual ring pattern of the wood grain pattern. For example, the pattern shape is a wood channel groove pattern.
Needless to say, the synchronized pattern may be an abstract pattern or the like depending on the application.

[Picture Layer] Even in a configuration in which a recoatable ionizing radiation-curable resin layer and a transparent resin layer are simply formed on a substrate, the design feeling of the substrate itself and the surface gloss state of the transparent resin layer (glossy, glossy) It is not necessary to provide a picture layer as long as the desired design feeling as a decorative material can be expressed by erasing or the like. However, usually, the picture layer 2 is provided in order to express the picture by printing or the like to obtain a high design (see FIG. 1). The picture layer is
According to the desired design expression, required physical properties, and the like, it may be formed by a conventionally known forming method and material for the decorative material, and there is no particular limitation.

If the pattern layer 2 is divided into a partial formation and a whole formation, the pattern layer 2 is partially formed to express an arbitrary pattern shape as exemplified in FIGS. 1A to 1C. It can be classified into a pattern pattern layer 2B and an entire solid layer 2A formed on the entire surface. All solid layer 2A and pattern pattern layer 2
B may be used alone, but usually, it is generally used in combination with the entire solid layer 2A as a base and the pattern pattern layer 2B formed thereon to express a pattern pattern. Many.

The picture layer 2 may be formed by a conventionally known forming method and material such as gravure printing, silk screen printing, offset printing, electrophotographic copying, and hand drawing (eg, brush drawing). The picture layer is usually a layer colored by adding a pigment. The pattern represented by the pattern layer is arbitrary, and includes, for example, a wood pattern, a stone pattern, a cloth pattern, a tile pattern, a brick pattern, a leather pattern, a character, a geometric pattern, and the like according to the application. In addition, all the solid layers which become the whole solid among the picture layers are:
It can also be formed with a paint by a known coating method such as a gravure coat or a roll coat.

Ink (or paint) for forming a picture layer
Consists of a vehicle such as a binder, a colorant such as a pigment or a dye, and various additives appropriately added thereto, similarly to a general ink (or paint). For the binder resin, for example, chlorinated polyolefin resin, polyester resin,
A general-purpose resin such as an acrylic resin, a cellulose resin, a vinyl chloride-vinyl acetate copolymer, a polyurethane resin, or the like can be selected and used alone or as a mixture containing these. However, a nitrocellulose-based resin or an acrylic resin-based resin is preferable as the binder resin from the viewpoint of adhesion to the recoatable ionizing radiation-curable resin layer.

Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, and quinacridone. , Permanent Red 4R, phthalocyanine blue, indasulene blue RS, aniline black and other organic pigments (or dyes), aluminum, brass, and other metal pigments, titanium dioxide-coated mica, basic lead carbonate and other foil powders. A pearlescent (pearl) pigment or the like may be used.

The pattern layer 2 may be a metal thin film layer or the like.
The metal thin film layer is formed of aluminum, chromium, gold, silver,
Using a metal such as copper, a film is formed by a method such as vacuum deposition or sputtering. Alternatively, a combination of these may be used. Even if the metal thin film layer is provided on the entire surface (to become the entire solid layer 2A),
Alternatively, it may be partially provided in a pattern (to become the pattern pattern layer 2B).

[Matte Layer] As shown in FIG. 1 (C), the partially formed transparent resin layer is formed with a glossy transparent resin layer 4A on the surface thereof. A matting layer 6 may be provided so as to be exposed at a portion where the transparent resin layer 4A is not formed. Since the matting layer 6 is exposed in the unformed portion of the glossy transparent resin layer 4A, the pattern of the surface gloss is
Further, the design feeling and the surface texture are improved. For example, the picture layer has a wood grain pattern, and the unformed portion of the transparent resin layer has a wood grain conduit pattern,
Since the conduit portion forms a matt concave portion, excellent conduit design expression is possible. Therefore, excellent design feeling and surface texture can be obtained. Note that the matte layer 6 has a picture layer on the lower side, or has no picture layer but uses the surface color or pattern of the substrate itself for design expression. . Note that the term “transparent” may refer to a colored and transparent colorant added.

The ink or coating solution for forming the matte layer is a general-purpose resin as a binder resin, for example,
Resins such as urethane resins, cellulosic resins, and polyester resins can be used. In order to achieve matting, an ink or coating liquid in which an extender such as silica, barium sulfate, or calcium carbonate is added in an amount of about 1 to 30 parts based on 100 parts by weight of a resin component may be used. The resin used for the matte layer is preferably a curable resin when surface properties such as solvent resistance, stain resistance, and scratch resistance are taken into consideration. The curable resin is, for example, a two-component curable resin, and the two-component curable resin is, for example, a two-component thermosetting urethane resin. The two-part thermosetting urethane resin may use a general-purpose curing agent such as tolylene diisocyanate.

[0047]

EXAMPLES Hereinafter, the abrasion-resistant decorative material of the present invention will be further described with reference to examples. In the following, "part"
All are based on mass.

Example 1 A decorative material D having a layer structure as shown in FIG. 1A was produced as follows. As a decorative base paper as a sheet-shaped base material 1, on one side of a resin-impregnated paper impregnated with an acrylic resin latex, as a picture layer 2, a 2 μm-thick solid layer (colored solid layer) 2A having a gravure printing method, The pattern pattern layer 2B was formed in this order. In addition, for all the solid layers, an ink was used in which a binder resin was a mixture of an acrylic resin and a nitrocellulose resin and a coloring agent was added. For the pattern pattern layer, an ink was used in which a binder resin was a mixture of a nitrocellulose resin and an alkyd resin, and a coloring agent was added. Next, a coating film having a thickness of 25 μm is formed by using the following (electron beam-curable) recoatable ionizing radiation-curable resin coating material, and then irradiated with an electron beam using an electron beam irradiation device to crosslink the coating film. By curing, a recoating ionizing radiation-curable resin layer 3 containing alumina as a filler 5 was formed.

Recoatable ionizing radiation curable resin paint Urethane acrylate 30 parts Bifunctional acrylate oligomer 20 parts Trifunctional acrylate oligomer 10 parts Silicone acrylate 3 parts Spherical α-alumina (average particle size 25 μm) 20 parts

Next, on the recoatable ionizing radiation-curable resin layer, the following two-component curable urethane-based top coat agent was applied over the entire surface by a gravure coating method to form a transparent resin layer 4 having a thickness of 3 μm. Subsequently, the transparent resin layer was completely cured by heating and drying at 60 ° C. for 3 days to obtain a decorative material D as a decorative sheet as shown in FIG. 1A.

Two-part curable urethane-based topcoat agent Alkyd-modified acrylic polyol 100 parts Modified polyisocyanate 15 parts Slip agent (silicone oil) 5 parts Diluent solvent (ethyl acetate + toluene) Appropriate amount

Example 2 A decorative material D having a layer structure as shown in FIG. 1B was prepared as follows. In Example 1, the formation of the transparent resin layer 4 formed on the recoatable ionizing radiation-curable resin layer 3 was performed by setting the wood grain conduit portion represented by the pattern pattern layer 2A of the picture layer 2 to an unformed portion. A decorative material D was produced in the same manner as in Example 1, except that the formation of the transparent resin layer 4A having a thickness of 3 μm was changed. The formation of the transparent resin layer 4A is performed using a gravure printing plate in which a portion other than the portion corresponding to the wood grain conduit is engraved using the same two-liquid thermosetting urethane resin-based top coating agent as in Example 1 as a gravure ink. And formed by gravure printing.

Example 3 A decorative material D having the structure shown in FIG. 1C was produced as follows. In Example 2, after forming the recoating ionizing radiation-curable resin layer 3 and before forming the transparent resin layer 4A, a matte layer 6 was applied over the entire surface. For the matting layer 6, a matting coating solution containing butyral resin as a binder resin and containing silica as a matting agent was used. Next, the surface protective layer 4 was formed by changing the gravure ink (top coat agent) used for the surface protective layer 4A in Example 2 to the following ionizing radiation-curable resin ink to form the surface protective layer 4. Similarly, a decorative material D was prepared.

Ionizing radiation curable resin ink bisphenol A ethylene oxide-modified diacrylate 50 parts Trimethylolpropane ethylene oxide-modified triacrylate 40 parts Amorphous silica (average particle size 1.8 μm) 8 parts Fine powder silica (average particle size 0. 1 μm) 1 part Both ends methacrylate-modified silicone 1 part

Comparative Example 1 A decorative material was prepared in the same manner as in Example 1, except that the formation of the recoating ionizing radiation-curable resin layer was omitted.

[Comparative Example 2] In Example 1, instead of forming the recoatable ionizing radiation-curable resin layer 3 and the transparent resin layer 4 after forming the picture layer 2 on the substrate 1, Using an ionizing radiation-curable resin paint as described above, a decorative material having an ionizing radiation-curable resin layer having a thickness of 25 μm as the outermost layer was prepared.

Ionizing radiation curable resin paint Bisphenol A ethylene oxide-modified diacrylate 50 parts Trimethylolpropane ethylene oxide-modified triacrylate 20 parts Spherical α-alumina (average particle diameter 25 μm) 20 parts Amorphous silica (average particle diameter 1.8 μm) 8 parts Fine powder silica (Average particle size 0.1 μm) 1 part Both ends methacrylate modified silicone 1 part

Comparative Example 3 A decorative material was prepared in the same manner as in Example 1, except that the formation of the transparent resin layer 4 was omitted (heating at 60 ° C. for 3 days was also omitted).

[Evaluation of Performance] The abrasion resistance and surface slipperiness as surface roughness were evaluated in the following manner, and the results shown in Tables 1 and 2 were obtained.

Abrasion resistance: Test evaluation was carried out according to a method according to JIS K6902 (Testing method for decorative board of thermosetting resin). Surface slipperiness: The cotton cloth was pressed against it with a load of 30 kPa and rubbed 10 times back and forth over a distance of 10 cm, and the degree of damage of the cotton cloth was visually evaluated.

[0061]

[Table 1]

[0062]

[Table 2]

As shown in Table 1, the examples (Example 1) have improved abrasion resistance as compared with the comparative examples (Comparative Example 2 and Comparative Example 3) and have no problem in practical use. As shown in Table 2, the surface slipperiness was good and the surface had a smooth surface. Comparative Example 2 has good abrasion resistance as in Example 1, but has poor surface slipperiness.

In addition, the design was also improved in Examples 2 and 3.
And the surface design effect (grain pattern reproducibility) of Comparative Example 3 was evaluated by visual observation. As a result, as compared with Comparative Example 3 in which the transparent resin layer was omitted, Example 2 having the transparent resin layer 4A having an unformed portion tuned to the grain pipe pattern of the picture layer,
It was a higher design. Further, in Example 3 in which the matting layer 6 was provided immediately below the transparent resin layer 4A, the wood grain conduit portion was a matted concave portion, and a design feeling closer to the real thing was obtained.

[0065]

According to the abrasion-resistant decorative material of the present invention, a filler for improving abrasion resistance is contained in the inner layer of the ionizing radiation-curable resin layer, and the resin layer is recoated. Since a transparent resin layer is formed thereon by coating as a recoatable ionizing radiation-curable resin layer, it is particularly excellent in abrasion resistance and does not have a rough surface due to the addition of a filler. Therefore, excellent abrasion resistance can be obtained without causing a problem of damaging or abrading an object that comes into contact with the surface for interior use (horizontal surface) or the like. Further, by using a thermosetting resin for the transparent resin layer, excellent abrasion resistance can be obtained inexpensively and simply. Also, by using an ionizing radiation-curable resin for the transparent resin layer, extremely excellent wear resistance can be obtained.

If a pattern layer is provided between the substrate and the layer of the recoating ionizing radiation-curable resin, the design becomes more sophisticated,
As a result of the picture layer being protected by the recoating ionizing radiation-curable resin, the wear resistance of the picture layer becomes extremely excellent. Further, if the transparent resin layer is formed so that the unformed portion is tuned to the pattern of the pattern layer, the surface unevenness due to the presence or absence of the transparent resin layer, and the synchronization between the unevenness and the pattern of the pattern layer. Depending on the feeling, a better design feeling and surface texture can be expressed. For example, the picture layer has a wood grain pattern, and the unformed portion of the transparent resin layer has a wood grain pipe pattern. Furthermore, if a matting layer is provided under the transparent resin layer having the unformed portion, the design feeling and the surface texture can be further improved by the pattern due to the difference in surface gloss between the transparent resin layer and the matting layer. For example, the wood grain conduit portion has a matte wood grain design.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating some embodiments of a wear-resistant decorative material according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base 2 Pattern layer 2A All solid layer 2B Pattern pattern layer 3 Recoatable ionizing radiation-curable resin layer 4 Transparent resin layer 4A Transparent resin layer (tuned with the pattern layer) 5 Filler 6 Matting layer D Cosmetic material

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) B32B 27/00 B32B 27/00 E B44C 3/02 B44C 3/02 A F-term (reference) 4D075 CA02 CA34 CB02 CB11 DC02 DC31 DC38 EA19 EA21 EA43 4F100 AA19B AA19H AK01B AK01C AK25A AK25B AK51C AK51D AR00D AT00A BA03 BA04 BA07 BA10A BA10C BA13 CA23B DC11C DG10A GB08 GB81 HB00 JB13JB13 JB13

Claims (6)

[Claims] 1. A recoatable ionizing radiation-curable resin, comprising: a recoatable ionizing radiation-curable resin layer on a substrate; and a transparent resin layer on the outermost surface of the recoatable ionizing radiation-curable resin layer. A wear-resistant decorative material in which the layer contains a filler. 2. The abrasion-resistant decorative material according to claim 1, wherein the transparent resin layer is made of an ionizing radiation-curable resin. 3. The wear-resistant decorative material according to claim 1, wherein the transparent resin layer is made of a thermosetting resin. 4. The wear-resistant decorative material according to claim 1, further comprising a picture layer between the substrate and the recoatable ionizing radiation-curable resin layer. 5. The abrasion-resistant decorative material according to claim 4, wherein the transparent resin layer is formed so that an unformed portion thereof is synchronized with the pattern of the pattern layer. 6. A mat formed on the recoatable ionizing radiation-curable resin layer so as to be formed closer to the substrate than the transparent resin layer having an unformed portion and to be exposed at least in the unformed portion. The wear-resistant decorative material according to claim 5, which has a layer.