JP2007247386A - Floor material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor material hardly dented, excellent in physical properties such as scratch resistance, wear resistance, antistaining performance and water resistance and further, particularly excellent in surface smoothness. <P>SOLUTION: The floor material comprises a hard layer consisting of a composition containing chemically-treated wood flour and a resin component and formed on one face of a plywood and a decorative material laminated on the hard layer via an adhesive layer. The chemically-treated wood flour is fibrous and the length of fibers is 50-200 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a floor material excellent in various physical properties such as caster resistance, drop impact resistance, scratch resistance, abrasion resistance, stain resistance, and water resistance, and particularly relates to a floor material excellent in surface smoothness. is there.

Conventionally, a flooring material in which a decorative material, for example, a decorative material provided with a wood grain pattern or the like on a sheet base material made of a veneer or paper or a synthetic resin, is known. The decorative material used for the flooring is usually made of a curable resin on the surface for the purpose of ensuring the surface properties required for the flooring, that is, scratch resistance, abrasion resistance, stain resistance, water resistance, etc. A surface protective layer is provided.

Moreover, as a wood-type base material, the composite material which laminated | stacked the medium density fiber board (MDF) on the surface of the plywood and the plywood is generally used. For flooring using plywood, when a load is applied to the caster part of furniture with casters or the leg tip part of a chair, desk, etc., the problem of being easily damaged by dents and the unevenness of the plywood surface are directly on the decorative sheet There is a problem (see, for example, Patent Document 1) that it appears on the surface of the film and the design properties are likely to be impaired. The flooring made of composite material is less susceptible to dents and scratches than the flooring made of a single piece of plywood, but swells by absorbing water, and the surface of the floor is likely to be corrugated, so that water is likely to scatter on the floor. There is a problem that it is hard to use in the kitchen.

  Therefore, instead of using a medium density fiberboard (MDF), a thermosetting composition composed of at least chemically treated wood flour and a thermosetting resin is placed on a wooden substrate such as plywood, Further, there is known a decorative board manufactured by placing a decorative material such as ordinary decorative paper or a decorative veneer on which a thermosetting resin in an uncured state can permeate and permeate, and then hot pressing it. (For example, refer to Patent Document 2).

The decorative board described in Patent Document 2 is a cosmetic material in which a wood substrate and an uncured thermosetting resin can permeate and permeate using a thermosetting composition containing chemically treated wood flour as an adhesive. Are integrated by heat pressure. Such a decorative board is excellent in surface hardness.

  However, there is a possibility that the thermosetting resin may not penetrate to the surface of the decorative material, and there is a possibility that the layers of the decorative material may be peeled off, or contamination resistance, water resistance, scratch resistance, and abrasion resistance are not good. There is a problem that it is enough. It is desired to solve these problems.

Further, the decorative board has a problem that unevenness of wood powder appears on the surface, that is, a so-called duck problem. It is also desired to solve such design problems.
JP 2001-193267 A Japanese Patent Laid-Open No. 9-48090

Therefore, the present invention provides a flooring material that is particularly resistant to dents and has excellent surface smoothness as well as excellent physical properties such as scratch resistance, abrasion resistance, stain resistance, and water resistance. is there.

In order to achieve the above object, the inventor of the present invention provides the flooring of the present invention according to claim 1 with a hardness imparting formed on one surface of a plywood by a composition containing chemically treated wood flour and a resin component. A flooring in which a decorative material is laminated on the hardness imparting layer via an adhesive layer, wherein the chemically treated wood flour is fibrous, and the fiber length is 50 μm or more and 200 μm or less It is characterized by this.

  The present invention according to claim 2 is the flooring according to claim 1, wherein the resin component is a thermosetting resin.

  The present invention according to claim 3 is the flooring according to claim 1 or 2, wherein the decorative material is a decorative sheet including a synthetic resin sheet base material.

According to a fourth aspect of the present invention, in the flooring according to the third aspect, the synthetic resin sheet base material is made of an olefinic thermoplastic resin.

  The invention according to claim 5 is the flooring according to claim 1 or 2, wherein the decorative material is a decorative sheet including a paper-based sheet base material.

  Moreover, the present invention according to claim 6 is characterized in that in the flooring according to claim 1 or 2, the decorative material is a protruding plate.

The present invention according to claim 7 is characterized in that, in the flooring according to claim 1, the decorative material includes a surface protective layer on the surface layer thereof.

The present invention according to claim 8 is the flooring according to claim 7, wherein the surface protective layer is made of an ionizing radiation curable resin.

  The present invention according to claim 9 is the flooring material according to claim 7 or 8, wherein the surface protective layer is a layer containing fine particles.

  The flooring of the present invention is provided with a hardness-imparting layer formed of a composition containing chemically treated wood flour and a curable resin on one surface of a plywood, and is decorated on the hardness-imparting layer via an adhesive layer. By providing the material and setting the fiber length of the chemically treated wood powder to 50 μm or more and 200 μm or less, the hardness as a flooring material can be increased, and caster resistance and drop impact resistance are imparted to the flooring material. be able to. Therefore, the flooring material of the present invention is not easily damaged.

  Moreover, the flooring of this invention has the outstanding water resistance by employ | adopting the said structure.

The flooring of the present invention has a design with excellent surface smoothness because the hardness-imparting layer absorbs the irregularities of wood flour and plywood.
The flooring of the present invention has a surface protective layer, in particular, a surface protective layer made of an ionizing radiation curable resin, provided on the surface of the decorative material. Water resistance).

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention, and FIG. 2 is a diagram illustrating a first embodiment of a decorative material having a surface protective layer on the surface layer constituting the flooring of the present invention. FIG. 3 is a layer configuration diagram schematically showing a second embodiment of a decorative material having a surface protective layer on the surface layer constituting the floor material of the present invention, and FIG. 4 is a floor material of the present invention. Is a layer configuration diagram schematically showing a third embodiment of a decorative material provided with a surface protective layer on the surface layer constituting 1, in which 1 is a flooring, 2 is a decorative material, 3 and 13 are adhesive layers,
5, 5 ', 5 "are primer layers, 6 are uneven patterns, 7 are wiping inks, 8 is a pattern printing layer, 8' is a solid pattern printing layer, 11 is a plywood, 12 is a hardness imparting layer, and 21 is a surface protective layer , 22 is a synthetic resin transparent layer, 22 ′ is a synthetic resin sheet, 23 is a paper-based sheet, and α is a fine particle.

  FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention. The flooring 1 is provided with a hardness imparting layer 12 formed of a resin containing chemically treated wood flour on one surface of a plywood 11, and a surface protection is provided on the surface of the hardness imparting layer 12 via an adhesive layer 13. The decorative material 2 having the layer 21 is laminated.

Examples of the plywood 11 include a plywood made of a southern sea material typified by a lauan material, a pine material, a cedar material, a cypress material, or the like. The plywood 11 is formed by arranging a plurality of single plates having different fiber directions for each layer, for example, three layers, five layers, or seven layers, and the fiber directions of the surface layers of the plurality of layers are parallel to the longitudinal direction of the plywood. Or the fiber layer direction of the surface layer may be configured in a direction perpendicular to the longitudinal direction of the plywood. Although not shown, normally, a side part of the plywood 11 is provided with a real part (female, male). The plywood 11 is laid on the floor foundation by fitting the female and male berries.

Further, the hardness imparting layer 12 absorbs surface irregularities and fluff of the plywood 11 and has a hardness to make the flooring 1 difficult to be dented, that is, imparts impact resistance and caster resistance. To be provided. The hardness imparting layer 12 is mainly composed of a resin and chemically treated wood flour. Any resin can be used without particular limitation as long as it can uniformly disperse and mix chemically treated wood flour. For example, polyethylene, polypropylene, butene-1, vinyl acetate, ethylene-vinyl acetate copolymer, acrylic, polyester, styrene, butadiene, acrylate-styrene copolymer, styrene-butadiene copolymer, acrylate-styrene -Thermoplastic resins such as butadiene copolymers, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins And thermosetting (thermosetting type) resins such as melamine-urea co-condensation resin, silicon resin, and polysiloxane resin. These resins are mixed with one or more thermoplastic resins and / or one or more thermosetting resins in consideration of processability, productivity, plywood penetration, layer hardness, etc. May be used. In consideration of obtaining higher hardness, it is preferable to use a mixture of one or more thermosetting resins without using a thermoplastic resin. If necessary, at least one additive selected from the group consisting of a curing agent such as a crosslinking agent and a polymerization initiator and a polymerization accelerator is added to the thermosetting resin. For example, isocyanate or organic sulfonate is added to the unsaturated polyester resin or polyurethane resin as a curing agent. An organic amine or the like is added to the epoxy resin as a curing agent. A peroxide such as methyl ethyl ketone peroxide, a radical initiator such as azoisobutyl nitrile, and a polymerization accelerator such as cobalt naphthenate are added to the unsaturated polyester resin.

Further, the chemically treated wood flour is contained in order to make a layer having higher hardness than the layer formed of the above-described resin alone due to a synergistic effect with the above-described resin. The chemically treated wood flour is obtained by reacting a chemical substance with a hydroxyl group in a wood material, and imparting thermoplasticity that was not originally provided to the wood material itself. For example, JP-A-57-103804, JP-A-58-32807, JP-A-60-188401, JP-A-60-206602, or Nobuo Shiraishi: Journal of the Wood Society of Japan vol. 32, no. 10, P755-762 (1986), Makoto Ohkoshi: Journal of the Wood Society of Japan vol. 36, no. 1, P57-63 (1990), etc., esterified wood, etherified wood, acetylated wood, allylated wood, benzylated wood, lauroylated wood, ethylated wood, cyanoethylated wood, and more Oligoesterified wood in which a dibasic acid anhydride and a monoepoxy compound having a polymerizable double bond are reacted with a hydroxyl group in a wood component disclosed in Kaihei 2-145339, and acetylcellulose, ethylcellulose, carboxy Cellulose derivatives such as methyl cellulose can be used. Preferably, it is an oligoester wood material because the production process is simple and there are no by-products that need to be removed from the system after the reaction. In addition, the woody material used as the raw material for the chemically treated wood flour is not particularly limited, such as tree species, wood powder, wood fiber, wood chips and other crushed wood, cellulose, pulp, or unused For example, plant fibers such as wheat straw, rice straw, straw pattern, waste paper, linter, bagasse, etc., or other pulverized lignocellulose materials mainly composed of cellulose or lignin may be used.
The chemically treated wood flour is fibrous and has a fiber length of 50 μm or more and 200 μm or less. From the viewpoint of increasing the hardness, it is preferable that the wood flour (fibers) are entangled with each other. From this point of view, it is preferable that the fiber is long. However, if the fiber is too long, the unevenness of the fiber may appear on the flooring surface, which is not preferable in the design. The fiber length can be measured, for example, by sieving wood flour.

The resin and the chemically treated wood flour are mixed with a known kneader. In the hardness imparting layer 12, the blending ratio of the resin and the chemically treated wood powder is 50 to 95 parts by weight as the resin, preferably 65 to 90 parts by weight, and the chemically treated wood powder is 50 to 5 parts by weight, preferably 35. It is preferably 10 to 10 parts by weight, and is preferably formed from a composition blended so that the total amount is 100 parts by weight. The hardness of the hardness-imparting layer 12 can be increased as the blending ratio of the chemically treated wood flour increases. If the blending ratio is too high, a mixture of resin and chemically treated wood flour cannot be applied by a highly productive coating method, such as a roll coating method or a gravure coating method. The blending ratio of the resin to the resin is naturally limited. The coating amount of the resin and the chemically treated wood powder mixture is suitably about 100 to 250 g / m ^{2 in} solid content, and preferably 120 to 250 g / m ² .

  For example, the hardness imparting layer 12 is formed by applying a mixture mainly composed of a thermosetting resin and chemically treated wood powder to one surface of a plywood by a roll coating method, and sandwiching the mixture from above and below by a metal mirror plate. It is formed by curing the mixture by hot pressing. When forming the hardness imparting layer 12, the hardness imparting layer 12 is integrated with the plywood 11.

The adhesive that forms the adhesive layer 13 may be appropriately selected depending on the material constituting the surface of the hardness imparting layer 12 and the decorative material 2 that contacts the adhesive layer. For example, a known adhesive such as a vinyl acetate resin, a urea resin, or a urethane resin (including a moisture curable hot melt adhesive) may be selected and used. The coating amount is generally 20 to 50 g / m ^{2 in} terms of solid content.

Next, the decorative material 2 having the surface protective layer 21 will be described. FIG. 2 is a layer configuration diagram schematically showing a first embodiment of a decorative material provided with a surface protective layer on the surface layer constituting the floor material of the present invention.
The decorative material 2 is embossed on one surface of a synthetic resin transparent layer 22 as a synthetic resin sheet base material to provide a concavo-convex pattern 6, and a wiping process is performed on the embossed pattern 6 in the concave portion of the concavo-convex pattern 6. After filling the wiping ink 7, the primer layer 5 is provided on the entire exposed surface, and the pattern printing layer 8 and the solid pattern printing layer 8 ′ are sequentially arranged on the other surface of the synthetic resin transparent layer 22 through the primer layer 5 ′. A decorative sheet made of a synthetic resin sheet base material formed by printing, wherein a surface protective layer 21 made of a curable resin is formed on the primer layer 5 of the decorative sheet.

FIG. 3 is a layer configuration diagram schematically showing a second embodiment of a decorative material provided with a surface protective layer on the surface layer constituting the floor material of the present invention. The decorative material 2 is provided with a primer layer 5 ″ on at least one surface of a synthetic resin sheet 2 ′ as a synthetic resin sheet base, and a solid pattern printing layer 8 ′ and a pattern printing layer 8 are provided on the primer layer 5 ″. A transparent layer 22 made of a synthetic resin is laminated on the entire surface on the pattern printing layer 8 side through an adhesive layer 3 formed of a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component. Then, the surface of the synthetic resin transparent layer 22 is embossed to provide a concavo-convex pattern 6, and then, similarly to the decorative material 2 shown in FIG. A decorative sheet made of a synthetic resin sheet base material in which the wiping ink 7 is filled in the recesses and the primer layer 5 is further provided on the surface, and a curable resin is formed on the primer layer 5 of the decorative sheet. It is obtained by forming a surface protective layer 21 that. As the synthetic resin sheet 22 ′, a colored sheet is generally used, but an uncolored sheet may be used. 2 and 3 show the embossing and wiping process as an embodiment of the decorative material 2, but the decorative material 2 used in the present invention is not limited to this. The decoration material 2 may be a decoration material provided with a concavo-convex pattern made only of embossing, or may be a mirror-finished decoration material having no concavo-convex pattern.

FIG. 4 is a layer configuration diagram schematically showing a third embodiment of a decorative material having a surface protective layer on the surface layer constituting the floor material of the present invention. The decorative material 2 is a decorative sheet made of a paper-based sheet base material in which a solid pattern printing layer 8 ′ and a pattern printing layer 8 are sequentially printed on one surface of a paper-based sheet 23 as a paper-based sheet base material. A surface protective layer 21 made of a curable resin containing fine particles α is formed on the entire surface on the pattern print layer 8 side.

Next, various materials constituting the decorative material 2 will be described. First, as the resin constituting the synthetic resin transparent layer 22 and the synthetic resin sheet 22 ', it is excellent in processability and does not generate harmful gas during combustion. Medium-density polyethylene, high-density polyethylene, homopolypropylene, ethylene alpha olefin copolymer, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate Examples thereof include olefin-based thermoplastic resins such as copolymers, saponified ethylene-vinyl acetate copolymers, and mixtures thereof. In view of being relatively inexpensive, the olefin-based thermoplastic resin is preferable. The synthetic resin transparent layer 22 and the synthetic resin sheet 22 ′ may be in an unstretched state or in a state of being stretched in a uniaxial or biaxial direction. The thickness is about 60 to 300 μm. Further, these sheets may be subjected to well-known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on necessary surfaces as necessary.

Examples of the paper-based sheet 23 include thin paper, craft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like. Is mentioned. Further examples include inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber, and woven or non-woven fabrics using organic resins such as polyester and vinylon.

  The pattern print layer 8 and the solid pattern print layer 8 ′ can be formed using ink by a known printing method such as a gravure printing method, an offset printing method, or a silk screen printing method. Examples of the pattern printing layer 8 include a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, characters, symbols, line drawings, and various abstract pattern patterns. The solid pattern printing layer 8 ′ is solid printed with a coloring ink having a concealing property. 2 to 4, the configuration in which both the pattern printing layer 8 and the solid pattern printing layer 8 ′ are provided is shown, but a configuration in which either one is provided may be used.

Examples of the ink for forming the pattern print layer 8 and the solid pattern print layer 8 ′ include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene as a vehicle, polyester, polyurethane obtained from isocyanate and polyol, and polyacrylic. , Polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin, etc. are used in a mixture of one or more, and pigments, solvents, various auxiliary agents, etc. are added thereto An ink can be used. In consideration of environmental problems, the vehicle may be a non-chlorine vehicle in which one or two or more types such as polyester, polyurethane obtained from isocyanate and polyol, polyacryl, polyvinyl acetate, cellulose resin, polyamide resin and the like are mixed. More preferably, it is a mixture of one or two or more of polyester, polyurethane obtained from isocyanate and polyol, polyacryl, polyamide resin and the like. The above-described ink may be used for the wiping ink 7 as well.

Next, the surface protective layer 21 will be described. The surface protective layer 21 is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, stain resistance, water resistance, and weather resistance required for the decorative material 2 (see FIG. 1). As the resin for forming the surface protective layer 21, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is suitable. However, ionization is more preferable because of high surface hardness and excellent productivity. It is a radiation curable resin.

As the thermosetting resin, the same resin as described for the hardness imparting layer 12 can be used. You may add hardening agents, such as said crosslinking agent and a polymerization initiator, or a polymerization accelerator to a thermosetting resin. As the method for forming the surface protective layer 21, for example, the above-described thermosetting resin is adjusted to have a viscosity that can be applied, and is applied by a known coating method such as a roll coating method or a gravure coating method. Accordingly, it can be formed by drying and curing. As an application quantity, 5-200 g / m < ² > is suitable in general, Preferably it is 10-30 g / m < ² >.

  Next, the ionizing radiation curable resin will be described. An ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules. Examples of ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, and the like. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light 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 fluorescent lamp, or a metal halide lamp can be used. A wavelength range of 190 to 380 nm can be used as the wavelength of ultraviolet rays. As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam used is 100 to 1000 keV, preferably 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

As the ionizing radiation curable resin, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as epoxy group in the molecule, There are polymers or polymers. These monomers, prepolymers or polymers are used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and is usually an ultraviolet ray or an electron beam.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. Usually, a prepolymer having a molecular weight of about 10,000 or less is used. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. The acrylate and methacrylate can be used in common, but the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation. .

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  Examples of monomers having a radically polymerizable unsaturated group include (meth) acrylate compound monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol ( Me ) Acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2 -(Meth) acryloyloxypropyl hydrogen terephthalate and the like.

  Moreover, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyl Examples thereof include oxyethyl phosphate.

  As the monomer having a cationic polymerizable functional group, the above-mentioned prepolymer monomer having a cationic polymerizable functional group can be used.

When curing the above-mentioned ionizing radiation curable resin by irradiating with ultraviolet rays,
A photopolymerization initiator is added as a sensitizer. Photopolymerization initiators used for curing resin systems having radically polymerizable unsaturated groups include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, diphenyl sulfide. Benzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In addition, photopolymerization initiators used for curing resin systems having cationic polymerizable functional groups include aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonate esters, fluoroxyxonium diallyl iodides. Sil salts and the like can be used alone or as a mixture. In addition, generally the addition amount of these photoinitiators is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins. The application method and application amount of the ionizing radiation curable resin are the same as those of the thermosetting resin, and the description thereof is omitted.

Moreover, when providing the said surface protective layer 21 with further abrasion resistance and abrasion resistance, an inorganic substance and / or an organic substance are contained, for example. Examples of the inorganic substance include fine particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Examples of the particle shape include a spherical shape, an elliptical shape, a polyhedral shape, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Examples of organic substances include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 3 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles. Moreover, the mixing ratio of the fine particles to the curable resin forming the surface protective layer 21 is 1 to 80 parts by weight with respect to 100 parts by weight of the curable resin.

The surface protective layer 21 may have a known organic UV absorber such as benzotriazole, benzophenone, or triazine, a known light stabilizer such as a hindered amine, or the like, depending on the required physical properties, or Well-known additives such as antistatic agents and leveling agents can be added.

Next, the primer layers 5, 5 ′, 5 ″ will be described. The primer layer 5 is provided for the purpose of improving the adhesive strength between the synthetic resin transparent layer 22 and the surface protective layer 21. The primer layer 5 ′ is provided for the purpose of improving the adhesive strength between the synthetic resin transparent layer 22, the pattern printing layer 8, and the solid pattern printing layer 8 ′. The primer layer 5 ″ is made of the synthetic resin. It is provided for the purpose of improving the adhesive strength between the sheet 22 ′ and the solid print layer 8 ′. Hereinafter, the primer layers 5, 5 ′, and 5 ″ are collectively referred to as a primer layer. The primer layer includes (i) a copolymer of an acrylic resin and a urethane resin, and (ii) an isocyanate. Made of resin, that is,
The copolymer of acrylic resin and urethane resin (i) is composed of an acrylic polymer component having a hydroxyl group at the end (component A), a polyester polyol component having a hydroxyl group at both ends (component B), and a diisocyanate component (component C). Are mixed to form a prepolymer, and a chain extender such as diamine (component D) is further added to the prepolymer to extend the chain. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the terminal. The primer layer is obtained by reacting the terminal hydroxyl group of this acrylic-polyester urethane copolymer with the isocyanate (ii) and curing it.

  The component A is a linear acrylic ester polymer having a hydroxyl group at the terminal. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferable because it is excellent in weather resistance (particularly the property against photodegradation) and can be easily copolymerized with urethane. . The component A is an acrylic resin component in the copolymer, and those having a molecular weight of 5000 to 7000 (weight average molecular weight) are preferably used because of particularly good weather resistance and adhesiveness. Further, as the component A, only those having hydroxyl groups at both ends may be used. Further, those having a conjugated double bond remaining at one end may be mixed with those having a hydroxyl group at both ends. By mixing the acrylic polymer in which the conjugated double bond remains, the layer in contact with the primer layer, for example, the ionizing radiation curable resin of the surface protective layer 21 and the conjugated double bond of the acrylic polymer react. Therefore, the adhesiveness between the ionizing radiation curable resin can be improved.

Component B reacts with diisocyanate to form polyester urethane and constitutes a urethane resin component in the copolymer. As the component B, a polyester polyol having hydroxyl groups at both ends is used. The polyester polyol includes an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. Examples thereof include a derived polyester compound. Examples of the diol include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol, and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. Preferred as the polyester polyol is adipate-based polyester using adipic acid or a mixture of adipic acid and terephthalic acid as the acid component, particularly preferably adipic acid, and 3-methylpentanediol and 1,4-cyclohexanedimethanol as the diol component. is there.

  The urethane resin component formed by the reaction of the component B and the component C gives flexibility to the primer layer, and the primer layer and the synthetic resin transparent layer 22 or the synthetic resin sheet 22 ' Contributes to adhesion. Moreover, the acrylic resin component which consists of an acrylic polymer (component A) contributes to a weather resistance and blocking resistance in the said primer layer. In the urethane resin, the molecular weight of the component B may be within a range in which a urethane resin capable of sufficiently imparting flexibility to the primer layer is obtained. Adipic acid or a mixture of adipic acid and terephthalic acid And when using the polyester diol which consists of 1, 4- cyclohexane dimethanol, 500-5000 (weight average molecular weight) is preferable.

The component C is an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule. Examples of the diisocyanate include tetramethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4′-cyclohexyl. A diisocyanate etc. can be mentioned. As the diisocyanate component, isophorone diisocyanate is preferable in terms of excellent physical properties and cost. When the above-mentioned components A to C are reacted, the isocyanate group is excessive with respect to the equivalent ratio of the total hydroxyl group (which may be an amino group) of the acrylic polymer, polyester polyol and chain extender described below to the isocyanate group. To be.

When the above three components A, B and C are reacted at 60 to 120 ° C. for about 2 to 10 hours, the isocyanate group of the diisocyanate reacts with the hydroxyl group at the end of the polyester polyol to form a polyester urethane resin component and an acrylic polymer. A compound in which a diisocyanate is added to a terminal hydroxyl group is also mixed, and a prepolymer is formed in a state where excess isocyanate groups and hydroxyl groups remain. As a chain extender, for example, a diamine such as isophorone diamine or hexamethylene diamine is added to the prepolymer, and the isocyanate group is reacted with the chain extender to extend the chain. Thereby, an acrylic polymer component is introduce | transduced in the molecule | numerator of polyester urethane, and the acryl-polyester urethane copolymer of (i) which has a hydroxyl group at the terminal can be obtained.

While adding the isocyanate of (ii) to the acrylic-polyester urethane copolymer of (i), the coating liquid adjusted to the required viscosity in consideration of the coating method and the coating amount after drying is prepared. The primer layer can be formed by applying the prepared coating solution by a known coating method such as a gravure coating method or a roll coating method. Coating amount after drying of the coating solution is from 1 to 20 g / m ^2, preferably from 1 to 5 g / m ^2. In addition, this primer layer may be a layer to which an additive such as a filler such as silica powder, a light stabilizer, or a colorant is added as necessary. The isocyanate of (ii) may be any isocyanate that can be crosslinked and cured by reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (i). Group isocyanates can be used. In particular, aliphatic isocyanates are desirable from the viewpoint of preventing thermal discoloration and weather resistance. Specifically, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate monomer, or a multimer such as dimer or trimer thereof, or And polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols. In addition, in the decoration material 2 of FIG. 2, FIG. 3, although the thing of the structure which provided the primer layer (The layer shown by the code | symbol 5, 5 ', 5''on FIG. 2, 3) was shown, The decoration material 2 in Fig. 3 is a specification that meets the high level requirement as a flooring material.When the requirement level as a flooring material is low, these primer layers (reference numerals 5, 5 ', 5 in Figs. It is not always necessary to provide the layer indicated by “”. Further, in FIG. 4, it is described above between the paper-based sheet 23 and the solid pattern printing layer 8 ′, or between the solid pattern printing layer 8 ′ and the pattern printing layer 8 and the surface protective layer 21. A primer layer may be provided to improve the adhesive strength, or the solid pattern printing layer 8 ′ and the pattern printing layer 8 may be protected to meet the high level requirements.

Moreover, the said uneven | corrugated pattern 6 can be formed by a heat press, a hairline process, etc.
Examples of the pattern include a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain of grain, a hairline, a multi-row groove, a mirror surface, and the like.

  Heretofore, the description has been made with the decorative material 2 having the surface protective layer 21 provided on the surface layer, but the flooring of the present invention is not limited to this. For example, the decorative material 2 before forming the primer layer 5 and / or the surface protective layer 21 in FIGS. 2 and 3 is laminated on the hardness imparting layer 12 integrated with the plywood 11 via the adhesive layer 13. Then, the primer layer 5 and / or the surface protective layer 21 may be provided. Further, the surface protective layer 21 is provided after the decorative material 2 before forming the surface protective layer 21 in FIG. 4 is laminated on the hardness imparting layer 12 integrated with the plywood 11 via the adhesive layer 13. May be. In addition, although not shown, instead of the decorative material 2 shown in FIGS. 2 to 4, oak, oak, sen, beech, zelkova having a thickness of 0.15 to 0.7 mm, preferably 0.15 to 0.3 mm. A veneer of hardwood such as oak may be used. In this case, as a matter of course, the surface protective layer 21 is provided after the projecting plate is laminated on the hardness imparting layer 12 integrated with the plywood 11 via the adhesive layer 13. Although not shown, instead of the decorative material 2 shown in FIGS. 2 to 4, the above-mentioned protruding plate is bonded to one surface of the polypropylene film, embossed from the polypropylene film side, and thereafter You may use the laminated material which provided the surface protection layer which consists of curable resin on the polypropylene film surface. In addition, when using a veneer board, you may bond paper and a nonwoven fabric to the back surface (surface which becomes a plywood side) of a veneer board in consideration of dry crack prevention and workability.

Next, the present invention will be described in more detail with reference to the following examples.
[Production of decorative material (decorative sheet) of second embodiment]
A solid print layer having a thickness of 3 μm was formed on one surface of a colored polypropylene film having a thickness of 60 μm subjected to double-sided corona discharge treatment with an acrylic printing ink. On the solid pattern layer, a pattern printing layer composed of a grain pattern printing layer was formed by a gravure printing method with a two-component curable urethane printing ink. Thereafter, a urethane / nitrified cotton primer layer was formed on the other surface by a gravure printing method. Next, after forming a 2 μm-thick adhesive layer made of a two-component curable urethane resin on the pattern print layer surface, a polypropylene system in which a benzotriazole ultraviolet absorber and a hindered amine radical scavenger are added to the adhesive layer surface The thermoplastic elastomer was heated and melt-extruded with a T-die extruder to form a transparent resin layer having a thickness of 80 μm to produce an intermediate sheet.

  Then, the concave part was provided in the surface of the said transparent resin layer with the embossed plate of the wood grain conduit pattern. The concave portion is filled with a sepia-colored wiping ink made of acrylic-urethane resin (mainly acrylic polyol and isocyanate is added as a curing agent) and dried, and on top thereof is an acrylic / urethane block copolymer. A two-component curable urethane-based resin added with isocyanate as a curing agent was applied to form a transparent primer layer having a thickness of 2 μm. Next, a urethane acrylate ionizing radiation curable resin is applied to the entire surface of the transparent primer layer, and an electron beam (acceleration voltage: 175 KeV, irradiation amount: 5 Mrad) is irradiated to form a transparent surface protective layer having a thickness of 20 μm. A formed decorative sheet was prepared.

68 parts by weight of a resin composition [unsaturated polyester resin (manufactured by DH Material Co., Ltd.), wood powder (manufactured by Agrifuture Jyotsu Co., Ltd .: fiber length 50 μm) 32 parts by weight of an oligoesterified wood material produced from Chinese peanut powder) and 0.7 parts by weight of a polymerization initiator (partial butyl peroxyisopropyl carbonate) added to the total weight of these parts] 200g uniformly by the coating method
/ M ^{2 was} applied. Thereafter, hot pressing (temperature: 135 ° C., pressure: 1 kg / cm ² , time: 3 minutes) was performed with a multi-stage press machine to produce a composite material in which the plywood and the hardness-imparting layer were integrated. Next, after both the front and back surfaces of the composite material are sanded, an adhesive [Chuo Rika Kogyo Co., Ltd .: BA-10L (main agent) 100 parts by weight BA-11B (curing agent) 2 0.5 g by weight] was applied at 80 g / m ² · wet, and the decorative sheet was laminated on the coated surface. Then, the flooring was obtained by cold pressing (pressing time: 1 hour).

As a chemically treated wood flour, the fiber length made by Agrifuture Joetsu Co., Ltd. is 60
A flooring was obtained in the same manner as in Example 1 except that an oligoesterified wood material produced from μm tang wood powder was used.

The chemically treated wood flour has a fiber length of 11 made by Agrifuture Joetsu Co., Ltd.
A flooring was obtained in the same manner as in Example 1 except that an oligoesterified wood material produced from 0 μm tang wood powder was used.

As a wood powder that has been chemically treated, the fiber length made by Agrifuture Joetsutsu Co., Ltd. is 15
A flooring was obtained in the same manner as in Example 1 except that an oligoesterified wood material produced from 0 μm tang wood powder was used.

As a chemically treated wood flour, the fiber length made by Agrifuture Joetsu Co., Ltd. is 20
A flooring was obtained in the same manner as in Example 1 except that an oligoesterified wood material produced from 0 μm tang wood powder was used.

The chemically treated wood flour has a fiber length of 21 made by Agrifuture Joetsu Co., Ltd.
A flooring was obtained in the same manner as in Example 1 except that an oligoesterified wood material produced from 0 μm tang wood powder was used.

A polymerization accelerator (cobalt naphthenate “Co-NAPHTHENATE 6% SH” manufactured by Dainippon Ink & Chemicals, Inc.) was further added to the resin composition of Example 1 to a total weight part of the unsaturated polyester resin and the chemically treated wood flour. A resin composition was prepared by adding 5 parts by weight, and a flooring was obtained in the same manner as in Example 1 except that the coating amount of the resin composition was 200 g / m ² .

  The flooring materials of Examples 1 to 7 produced above were subjected to a caster test (* 1), the depth of the dent was measured and evaluated, and the results are shown in Table 1. In addition, the caster test was done also about the plywood single-piece | unit used for the present Example for reference, and the dent depth was measured.

* 1) Caster test:
A wheel made of polyamide with a diameter of 260 mm and an interval of 120 degrees (diameter: 75 mm, width: 25 mm
) Was applied to the jig provided with 3 kg, and a test was performed at a speed of 20 rpm by rotating the jig at a speed of 20 rpm for 1000 revolutions by reversing the direction of rotation every 5 minutes. Unit: μm) was measured. The smaller the dent depth, the better the caster resistance. In addition, as caster resistance evaluation, as a criterion of our company, dent depth of 100 μm or more is evaluated as “x”, less than 100 μm is evaluated as “good”, and dent depth of less than 20 μm is evaluated as “best” as ◎. The numerical value of the dent depth is an average value of 10 arbitrary measurement points on the floor material subjected to the caster test.

  As is clear from Table 1, the flooring materials of Examples 1 to 7 were preferable in caster resistance as compared with the plywood alone.

2) Confirmation of surface smoothness:
The surface smoothness of the flooring materials of Examples 1 to 7 was confirmed by confirming the feel of the surface protective layer of the flooring materials of Examples 1 to 7.

  The flooring materials of Examples 1 to 5 and 7 were found to have excellent surface smoothness. In addition, although the flooring material of Example 6 has surface smoothness to some extent, since the unevenness of the wood powder appears slightly on the surface of the decorative material (decorative sheet), the flooring material for which surface smoothness is required is used. There may be some problems.

It is a figure showing the basic layer composition of the flooring concerning the present invention diagrammatically. BRIEF DESCRIPTION OF THE DRAWINGS It is a layer block diagram which shows 1st Embodiment of the decorating material provided with the surface protection layer in the surface layer which comprises the flooring of this invention schematically. It is a layer block diagram which shows schematically 2nd Embodiment of the decoration material provided with the surface protection layer in the surface layer which comprises the flooring of this invention. It is a layer block diagram which shows diagrammatically 3rd Embodiment of the decoration material provided with the surface protection layer in the surface layer which comprises the flooring of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flooring material 2 Decoration material 3,13 Adhesive layer 5,5 ', 5 "Primer layer 6 Irregularity pattern 7 Wiping ink 8 Picture printing layer 8' Solid pattern printing layer 11 Plywood 12 Hardness-imparting layer 21 Surface protection layer 22 Synthetic resin Transparent layer 22 'Synthetic resin sheet 23 Paper-based sheet α Fine particles

Claims (9)

A flooring material in which a hardness imparting layer formed of a composition containing chemically treated wood flour and a resin component is provided on one surface of a plywood, and a decorative material is laminated on the hardness imparting layer via an adhesive layer. And
The flooring material characterized in that the chemically treated wood flour is fibrous and has a fiber length of 50 μm or more and 200 μm or less. The flooring according to claim 1, wherein the resin component is a thermosetting resin. The decorative material is a decorative sheet including a synthetic resin sheet base material.
Or the flooring of 2. The floor material according to claim 3, wherein the synthetic resin sheet base material is made of an olefin-based thermoplastic resin. The flooring according to claim 1 or 2, wherein the decorative material is a decorative sheet including a paper-based sheet base material. The flooring according to claim 1 or 2, wherein the decorative material is a protruding plate. The flooring according to claim 1, wherein the decorative material has a surface protective layer on a surface layer thereof. 8. The flooring according to claim 7, wherein the surface protective layer is made of an ionizing radiation curable resin. The flooring according to claim 7 or 8, wherein the surface protective layer is a layer containing fine particles.

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