WO2007091614A1

WO2007091614A1 - Flooring material

Info

Publication number: WO2007091614A1
Application number: PCT/JP2007/052153
Authority: WO
Inventors: Hiroshi Matsubara; Isao Yoshimura
Original assignee: Dai Nippon Printing Co., Ltd.
Priority date: 2006-02-07
Filing date: 2007-02-07
Publication date: 2007-08-16

Abstract

A flooring material that not only has resistance to dent flaw and excels in properties, such as scuff resistance, abrasion resistance, antistaining performance and water resistance, but also especially excels in surface smoothness. There is provided a flooring material characterized in that a hardness imparting layer consisting of a composition containing chemically treated wood flour and resin component is superimposed on one major surface of plywood, and that the hardness imparting layer is overlaid via an adhesive layer with an ornamental material.

Description

Specification

Flooring

Technical field

[0001] The present invention relates to a flooring material excellent in various properties such as caster resistance, drop impact resistance, scratch resistance, abrasion resistance, contamination resistance, and water resistance, and more particularly, a flooring material excellent in surface smoothness. It is about.

Background art

[0002] Conventionally, flooring materials have been known in which a decorative material such as a veneer or paper or synthetic resin is attached to a wooden base material, and a decorative material provided with a wood grain pattern or the like is attached to the wooden base material. . The above decorative material used for flooring is usually a curable resin on the surface for the purpose of ensuring the surface properties required for flooring, that is, scratch resistance, abrasion resistance, contamination resistance, water resistance, etc. A surface protective layer is provided.

[0003] Also, as the wood base material, a composite material in which a medium density fiberboard (MDF) is laminated on the surface of a plywood or a plywood is generally used. Plywood flooring is prone to dents and irregularities on the plywood surface when a load is applied to the caster part of furniture with casters or to the leg tips of chairs, desks, etc. There is a problem (see, for example, Patent Document 1) that it appears on the surface of the decorative sheet and tends to impair the design. The flooring made of composite material is less susceptible to dents and scratches than the flooring made of plywood alone, but it absorbs water and swells, making it easy for waviness to occur on the floor, so water is scattered on the floor. However, there are problems in the kitchen and the like.

[0004] Therefore, instead of using medium density fiberboard (MDF), a thermosetting composition comprising at least a chemically treated wood flour and a thermosetting resin is applied to a woody substrate such as plywood, for example. It is then manufactured by placing a decorative material such as a decorative decorative paper or a decorative veneer on which a thermosetting resin in an uncured state can permeate and permeate. There is a known decorative plate (see, for example, Patent Document 2).

[0005] The decorative board described in Patent Document 2 uses a thermosetting composition containing chemically treated wood flour as an adhesive, and a wooden substrate and an uncured thermosetting resin penetrated. Permeability A cosmetic material is integrated with heat pressure. Powerful decorative boards are excellent in surface hardness.

[0006] However, there is a possibility that the thermosetting resin does not penetrate to the surface of the decorative material, and there is a possibility that the layers of the decorative material may be peeled, or contamination resistance, water resistance, scratch resistance. There is a problem that the property and wear resistance are insufficient. It is desired to solve these problems. In addition, 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.

Patent Document 1: JP 2001-193267 A

Patent Document 2: JP-A-9-48090

Disclosure of the invention

Problems to be solved by the invention

[0007] Therefore, the present invention provides a flooring material that is particularly excellent in surface smoothness as well as being excellent in various physical properties such as scratch resistance, abrasion resistance, contamination resistance, and water resistance that are difficult to be dented. It is to be. Means for solving the problem

[0008] As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a flooring material having a specific configuration can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention relates to the following flooring material.

1. 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. Flooring.

2. The flooring according to item 1, wherein the chemically treated wood flour is fibrous and has a fiber length of 50 μm to 200 μm.

3. The flooring according to item 1 above, wherein the resin component is a thermosetting resin.

4. The hardness-imparting layer has a blending ratio of rosin and chemically treated wood powder of 65 to 90 parts by weight as rosin, 35 to LO as chemically treated wood powder, and 100 parts by weight as a total amount. Item 2. The flooring according to Item 1, wherein the flooring is formed from a composition formulated so as to be.

5. The flooring according to item 1, wherein the decorative material is a decorative sheet including a synthetic resin sheet base material. 6. The flooring according to 5 above, wherein the synthetic resin sheet substrate is made of an olefin thermoplastic thermoplastic resin.

7. The flooring according to item 1, wherein the decorative material is a decorative sheet including a paper-based sheet base material.

8. The flooring material according to any one of Items 1 to 4, wherein the decorative material is a veneer.

9. The flooring according to item 1, wherein the decorative material has a surface protective layer on the surface layer.

10. The flooring according to item 9 above, wherein the surface protective layer is made of ionizing radiation curable resin.

11. The flooring according to Item 9, wherein the surface protective layer is a layer containing fine particles.

The invention's effect

[0010] 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 an adhesive layer on the hardness-imparting layer The decoration material is provided through. By adopting such a configuration, the hardness of the flooring material can be increased, and caster resistance and drop impact resistance can be imparted to the flooring material. Therefore, the floor material of the present invention is hardly damaged by dents.

[0011] Further, the flooring of the present invention has excellent water resistance by adopting the above configuration.

[0012] The flooring of the present invention has a design with excellent surface smoothness because the hardness-imparting layer absorbs irregularities of wood flour and plywood.

The flooring of the present invention has excellent surface properties (scratch resistance, abrasion resistance, contamination resistance) by providing a surface protective layer, particularly a surface protective layer made of ionizing radiation curable resin, on the surface of the decorative material. Water resistance).

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The present invention will be described in detail below with reference to the drawings.

FIG. 1 is a diagram schematically showing the 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 floor material, 2 is a decorative material, 3 and 13 are adhesive layers, 5, 5 'and 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 with hardness 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 a is a fine particle.

FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention. A 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 layer is provided on the surface of the hardness imparting layer 12 via an adhesive layer 13. A decorative material 2 having a protective layer 21 is laminated.

[0015] Examples of the plywood 11 include a plywood having a strength such as a southern sea material typified by a lauan material, a pine material, a cedar material, and a cypress material. The plywood 11 is a single plate having different fiber directions arranged in multiple layers, for example, 3 layers, 5 layers, or 7 layers, and the fiber direction of the surface layer of the multiple layers is the longitudinal direction of the plywood. Either a parallel structure or a structure in which the fiber direction of the surface layer is formed in a direction perpendicular to the longitudinal direction of the plywood may be used. 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.

[0016] Further, the hardness imparting layer 12 absorbs the surface irregularities and fluff of the plywood 11, and has a hardness to make the flooring 1 difficult to be dented. Provided to provide star properties. The hardness imparting layer 12 is mainly composed of rosin and chemically treated wood flour. As the resin, any resin can be used as long as it can uniformly disperse and mix chemically treated wood flour. For example, polyethylene, polypropylene, butene-1, butyl acetate, ethylene acetate butyl 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-part curable polyurethanes), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins And thermosetting (thermosetting) resin such as melamine resin, guanamine resin, melamine-urea co-condensed resin, silicon resin, polysiloxane resin. These resins are one or more of thermoplastic resins in consideration of processability, productivity, penetration into plywood and layer hardness, and more and Z or 1 of thermosetting resins. A mixture of seeds and more may be used. In consideration of obtaining higher hardness, use thermoplastic resin It is preferable to use a mixture of more than one kind of thermosetting resin without any problems. 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, as a curing agent, isocyanate or organic sulfonate salt is added to unsaturated polyester resin, polyurethane resin, etc. An organic amine or the like is added to the epoxy resin as a curing agent. A radical initiator such as methyl isobutyl nitrile peroxide such as methyl ethyl ketone peroxide 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 single resin by synergistic effect with the above-described resin. Chemically treated wood flour is obtained by reacting a chemical substance with a hydroxyl group in a wood material, and giving the wood material itself a unique thermoplasticity. 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, P7 55 to 762 (1986), Makoto Ogoshi: Journal of the Wood Society vol. 36, No. 1, P57 to 63 (1990), etc. Esterified wood, etherified wood, acetylated wood , Arylated wood, benzylated wood, lauroylated wood, ethylated wood, cyanoethylated wood, and dibasic acid anhydride and polymerized hydroxyl group in the wood component disclosed in Japanese Patent Publication No. 2-145339 Oligoester wood obtained by reacting a monoepoxy compound having an ionic double bond, cellulose derivatives such as acetyl cellulose, ethyl cellulose, carboxymethyl cellulose, and the like can be used. An oligoester wood material is preferred 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 chemically treated wood flour includes pulverized wood such as wood flour, wood fiber, and wood chips that are not particularly restricted in shape, cellulose, norp, Non-used waste straw, rice straw, leopard pattern, waste paper, linter, bagasse and other plant fibers, or other pulverized lignocellulose materials based on cellulose and lignin . When the chemically treated wood flour is fibrous, the fiber length of the wood flour is not particularly limited. In order to increase hardness, wood flour ( The fibers) are preferably entangled with each other. In view of this meaning, it is preferable that the fiber is long. However, if the fiber is too long, the unevenness of the fiber may appear on the floor material surface, which is not preferable in the design. The fiber length of the wood flour is preferably 50 μm or more and 200 μm or less. The fiber length can be measured, for example, by sieving wood flour.

[0018] The resin and the chemically treated wood flour are mixed by a known kneader. The hardness-imparting layer 12 has a blending ratio of rosin and chemically treated wood flour of 50 to 95 parts by weight, preferably 65 to 90 parts by weight as rosin, and 50 to 5 parts by weight as chemically treated wood flour, preferably Is preferably 35 to 10 parts by weight, and it is also preferable that the compositional force is formulated so that the total amount is 100 parts by weight! The hardness of the hardness imparting layer 12 can be increased as the proportion of the chemically treated wood flour increases. If the blending ratio is too high, a mixture of rosin and chemically treated wood powder cannot be applied by a highly productive coating method such as a roll coating method or gravure coating method. Naturally, there is a limit to the blending ratio of the treated wood flour to the fat. The coating amount of the mixture of cocoa butter and chemically treated wood flour is generally about 100 to 250 g / m ² force for solids, and preferably 120 to 250 g / m ² force! / ヽ.

[0019] The hardness imparting layer 12 is formed by, for example, applying a mixture mainly composed of thermosetting resin and chemically treated wood powder on one surface of a plywood by a roll coating method, and then using a metal mirror plate. It is formed by curing the mixture by hot pressing from above and below. When forming the hardness imparting layer 12, the hardness imparting layer 12 is integrated with the plywood 11.

[0020] The adhesive forming the adhesive layer 13 may be appropriately selected and used depending on the material constituting the surface of the hardness imparting layer 12 and the decorative material 2 in contact with the adhesive layer. For example, a known adhesive force such as vinyl acetate-based resin, urea-based resin, urethane-based resin (including 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 formed by embossing one surface of a synthetic resin transparent layer 22 as a synthetic resin sheet base material to provide an uneven pattern 6 and then performing a wiping treatment on the surface to form the uneven pattern. After the wiping ink 7 is filled in the recesses of the surface 6, the primer layer 5 is provided on the entire exposed surface, and the pattern printing layer 8 is provided on the other surface of the synthetic resin transparent layer 22 via the primer layer 5 ′. A decorative sheet made of a synthetic resin sheet base material in which a solid print layer 8 ′ is printed in order, and a surface protective layer 21 made of a curable resin on the primer layer 5 of the decorative sheet. Is formed.

FIG. 3 is a layer configuration diagram schematically illustrating a second 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 synthetic resin sheet substrate. A primer layer 5 "is provided on at least one surface of the resin resin sheet 2 ', and a solid print layer 8' and a pattern print layer 8 are provided on the primer layer 5". In addition, a synthetic resin transparent layer 22 is formed through an adhesive layer 3 formed of a two-component curable polyurethane-based adhesive that also has a polyol component and an isocyanate component force on the entire surface on the picture print layer 8 side. Laminated and embossed on the surface of the synthetic resin transparent layer 22 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 a recess 6 of the pattern 6 is filled with wiping ink 7 and further provided with a primer layer 5 on the surface, and is cured on the primer layer 5 of the decorative sheet. Surface protective layer made of rosin 21 is formed. As the synthetic resin sheet 22 ′, a non-colored sheet that is generally a colored sheet may be used. 2 and 3 show the embellishment force and the wiping treatment as an embodiment of the decoration material 2, the decoration material 2 used in the present invention is not limited to this. The decorative material 2 may be a decorative material provided with a concave / convex pattern that is only embossed, or a mirror-finished decorative material without a concave / 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 that also has the strength 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 2 3 as a paper-based sheet base material, A surface protective layer 21 made of a curable resin containing fine particles oc is formed on the entire surface of the pattern printing layer 8 side.

Next, various materials constituting the decorative material 2 will be described. First, the resin constituting the synthetic resin transparent layer 22 and the synthetic resin sheet 22 ′ has excellent processability. Saturated polyester resin is low density polyethylene (including linear low density polyethylene), medium density polyethylene, high density polyethylene, homopolypropylene, ethylene α-olefin copolymer because it does not generate harmful gases during combustion. Olefin-based thermoplastic resin such as polymethylpentene, polypropylene, ethylene propylene copolymer, propylene-butene copolymer, ethylene vinyl acetate copolymer, ethylene vinyl acetate copolymer saponified product, or a mixture thereof Can be mentioned. Considering that it is 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 a stretched state in a uniaxial or biaxial direction. The thickness is approximately 60 to 300 μm. In addition, these sheets may be subjected to a known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on a necessary surface as necessary.

[0025] The paper-based sheet 23 includes thin paper, craft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfate paper, dalasin paper, parchment paper, paraffin. Examples include paper and Japanese paper. In addition, examples include inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber, and woven and tanned nonwoven fabrics using organic resin such as polyester and vinylon. it can.

[0026] Further, the pattern printing layer 8 and the solid pattern printing layer 8 'can be formed using ink by a known printing method such as a gravure printing method, an offset printing method, a silk screen printing method, or the like. 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 show the configuration in which both the pattern print layer 8 and the solid pattern print layer 8 ′ are provided, the configuration in which either one is provided may be used.

[0027] In addition, as the ink for forming the picture print layer 8 and the solid pattern print layer 8 ', a chlorinated polyolefin such as chlorinated polyethylene or chlorinated polypropylene, a polyester, an isocyanate and a polyol are also obtained. Polyurethane, polyacrylic, poly (vinyl acetate), polyvinyl chloride, butyl chloride, butyl acetate copolymer, cellulose resin, polyamide resin, etc. are used in combination with one or more, pigments, solvents, various Supplement An ink made by adding an auxiliary agent or the like can be used. In consideration of environmental issues, the vehicle is a non-mixed mixture of one or more of polyester, isocyanate and polyurethane that can also obtain polyol strength, polyacrylic, polyacetate butyl, cellulosic resin, polyamide resin, etc. A chlorine-based vehicle is suitable, and more preferably one or a mixture of two or more of polyesters, isocyanates, polyurethanes, polyacryls, polyamide-based resins and the like that can also obtain polyol power. 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 forming the surface protective layer 21, a curable resin such as a thermosetting resin or an ionizing radiation curable resin is suitable, but more preferably, the surface hardness is high and the productivity is excellent. The reason for this is ionizing radiation curable resin.

[0029] As the thermosetting resin, the same resin as described in the hardness imparting layer 12 can be used. A curing agent such as the above-mentioned crosslinking agent or polymerization initiator, or a polymerization accelerator may be added to the thermosetting resin. As the method for forming the surface protective layer 21, for example, the above-mentioned thermosetting resin is adjusted to have a viscosity capable of being applied, and is applied by a known application method such as a roll coating method or a gravure coating method. In addition, it can be formed by drying and curing as necessary. The coating amount is generally 5 to 200 g / m ² , and preferably 10 to 30 gZm ² .

[0030] 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 bridging molecules. Examples of ionizing radiation include visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, and ion beams. Usually, ultraviolet rays and 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. Also 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 amount of electron beam irradiation is usually about 2 to 15 Mrad.

[0031] The ionizing radiation curable resin has a radically polymerizable unsaturated group such as a (meth) atalyloyl group, a (meth) allyloyloxy group, or a cationic polymerizable functional group such as an epoxy group in the molecule. There are monomers, prepolymers or polymers. These monomers, prepolymers or polymers are used singly or in combination. In the present specification, the term “(meth) atalylate” is used to mean attalate or metaatarylate. The ionizing radiation means an electromagnetic wave or a charged particle beam having energy quanta that can polymerize or crosslink molecules, and is usually an ultraviolet ray or an electron beam.

[0032] Prepolymers having radically polymerizable unsaturated groups include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate. And polybulurpyrrolidone. 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. Although the above acrylate and meta acrylate can be used in common, the acrylate is faster in terms of crosslinking cure speed with ionizing radiation. Is more advantageous.

[0033] Examples of prepolymers having a cationically polymerizable functional group include bisphenol type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, and the like, aliphatic bull ethers, and aromatic bulls. Examples thereof include prepolymers such as ethers, urethane-based ethers, vinyl ether-based resins such as ester-based ethers, cyclic ether compounds, and spiro compounds.

[0034] Examples of the monomer having a radically polymerizable unsaturated group include a monofunctional monomer of a (meth) ataretoy compound, methyl (meth) acrylate, ethyl (meth) acrylate, Butyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxy butyl (meth) acrylate, butoxychetyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, N, N-dimethyl Ruaminomethyl (meth) acrylate, N, N Dimethylaminoethyl (meth) acrylate, N, N Jetylaminoethyl (meth) acrylate, N, N Jetylaminopropyl (meth) acrylate, N, N Di Benzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobol (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy ethyl (meth) acrylate, phenoxy polyethylene glycol ( (Meth) attalylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2-

Examples include (meth) attayllooxychetyl 2-hydroxypropyl phthalate, 2- (meth) attayloxypropyl hydrogen terephthalate, and the like.

[0035] The polyfunctional monomer having a radically polymerizable unsaturated group includes 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, trimethylol propane tri (meth) acrylate, trimethylol propane ethylene oxide tri ( Meta) Atarirate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate Rate, tris (meth) atarilooxychetyl phosphate, and the like.

[0036] As the monomer having a cationic polymerizable functional group, the monomer of a prepolymer having the cationic polymerizable functional group can be used.

[0037] When the above-mentioned ionizing radiation curable resin is cured by irradiating with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. Examples of photopolymerization initiators used for curing resin systems having radically polymerizable unsaturated groups include acetophenones, benzophenones, thixanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, Diphenylsulfide, dibenzyldisulfide, dimethylolite, triphenylbiimidazole, isopropyl N, N dimethylamino Benzoates and the like can be used alone or in combination. In addition, photopolymerization initiators used for curing a resin having a cationic polymerizable functional group include aromatic diazo-um salts, aromatic sulfo-um salts, meta-octene compounds, benzoin. A sulfonic acid ester, a freeroxyquinomyl allyldosyl salt, etc. can be used alone or as a mixture. The addition amount of these photopolymerization initiators is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin. 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.

[0038] Further, when the surface protective layer 21 is given further scratch resistance and wear resistance, for example, an inorganic substance and Z or an organic substance are contained. Examples of inorganic substances 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 a-alumina is particularly preferable because it has a high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles. Further, 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.

[0039] The surface protective layer 21 may be a known organic ultraviolet absorber such as a benzotriazole, benzophenone, or triazine or a hindered amine, depending on the required physical properties. Well known additives such as antistatic agents and leveling agents can be added.

[0040] 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 and the pattern printing layer 8 and the solid pattern printing layer 8 ′. "Is provided for the purpose of improving the adhesive strength between the synthetic resin sheet 22 'and the solid pattern printing layer 8'. Hereinafter, the primer layers 5, 5 ′ and 5 ″ are collectively referred to as a primer layer. The primer layer includes (i) acrylic resin and urethane resin. It is formed of a coconut resin comprising a copolymer with fat and (ii) isocyanate. In other words, the copolymer of (i) acrylic resin and urethane resin is composed of an acrylic polymer component having a hydroxyl group at the terminal (component A) and a polyester polyol component having a hydroxyl group at both ends (component). B) and diisocyanate component (component C) are mixed and reacted to form a prepolymer, and a chain extender such as diamine (component D) is added to the prepolymer to extend the chain. . As a result of 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 prepared by reacting the hydroxyl group at the end of the acrylic polyester urethane copolymer with the isocyanate of (ii) and curing it.

[0041] Component A is a linear acrylate polymer having a hydroxyl group at the terminal.

Specifically, linear polymethylmetatalylate (PMMA) having a hydroxyl group at the end is excellent in weather resistance (particularly the property against photodegradation), and can be easily copolymerized with urethane. It is preferable from a certain point. 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 their particularly good weather resistance and adhesiveness. Further, as the component A, only those having hydroxyl groups at both ends may be used. In addition, a compound in which a conjugated double bond remains at one end may be mixed with the one having a hydroxyl group at both ends as described above. 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 are formed. In order to react, the adhesion between the ionizing radiation curable resin can be improved.

[0042] 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. Examples of the polyester polyol include an aromatic dioli compound having a spiro ring skeleton and a ratatoni compound, an addition reaction product of a derivative thereof or an epoxy compound, a condensation product of a dibasic acid and a diol. Examples thereof include a combined product and a polyester compound derived from a cyclic ester compound. Examples of the diol include ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol. And short chain diols such as 1,4-cyclohexanedimethanol and the like. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like. Preferred as a polyester polyol is an adipate system using adipic acid or a mixture of adipic acid and terephthalic acid as an acid component, particularly 3-methylpentanediol and 1,4-cyclohexanedimethanol as a diol component preferred by adipic acid. Polyester.

[0043] 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. Contributes to adhesion with sheet 22 '. In addition, an acrylic polymer (an acrylic resin component composed of components contributes to weather resistance and blocking resistance in the primer layer. In urethane resin, the molecular weight of component B is flexible in the primer layer. As long as urethane resin can be provided, sufficient adipic acid or a mixture of adipic acid and terephthalic acid, polyester diol consisting of 3-methylpentanediol and 1,4-cyclohexanedimethanol 500 to 5000 (weight average molecular weight) is preferred.

[0044] The component C is an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule. Examples of the diisocyanate include tetramethylenediisocyanate, 2, 2, 4 (2, 4, 4) 1, 6 hexamethylene diisocyanate, isophorone diisocyanate, 4, 4'-dicyclohexylino. Examples include lemethane diisocyanate and 1,4′-cyclohexyl diisocyanate. 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 equivalent ratio of the total hydroxyl group (may be an amino group) of the acrylic polymer, polyester polyol and chain extender described below to the isocyanate group! The isocyanate group is excessive.

[0045] 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. As a result, a compound in which a diisocyanate was added to the hydroxyl group at the end of the acrylic polymer was also present, resulting in an excess of isocyanate groups and hydroxyl groups remaining. A state of prebolimer is formed. As a chain extender, for example, a diamine such as isophorone diamine, hexamethylene diamine and the like is added to this prepolymer and the isocyanate group is reacted with the chain extender to extend the chain. As a result, the acrylic polymer component is introduced into the polyester urethane molecule, and the (i) acrylic polyester urethane copolymer having a hydroxyl group at the terminal can be obtained.

[0046] The acrylic polyester urethane copolymer of (i) is covered with the isocyanate of (ii), and a coating solution is prepared that is adjusted to the required viscosity in consideration of the coating method and the coating amount after drying. To do. The primer layer can be formed by applying the prepared coating solution by a known coating method such as gravure coating or roll coating. Coating amount after drying of the coating solution is 1~ 20gZm ^2, preferably l~5gZm ^2. Further, 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. As the isocyanate of (ii), any isocyanate that can react with the hydroxyl group of the acrylic polyester urethane copolymer of (i) and be cured by crosslinking can be used. Isocyanates can be used. In particular, aliphatic isocyanates are desirable for preventing thermal discoloration and weather resistance. Specifically, tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylenomethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate monomer, or Examples thereof include multimers such as these dimers and trimers, and polyisocyanates such as derivatives (adducts) obtained by attaching these isocyanates to polyols. In addition, in the decorative material 2 in FIGS. 2 and 3, a force showing a configuration in which a primer layer (a layer indicated by reference numerals 5, 5 ′, and 5 ″ on FIGS. 2 and 3) is provided. The decorative material 2 in 3 is a specification that meets the high level requirements for flooring, and when the required level for flooring is low, these primer layers (Figs. 2 and 3 above, symbols 5, 5 ', 5 It is not always necessary to provide the layer indicated by “ Further, in FIG. 4, the paper-based sheet 23 and the solid pattern printing layer 8 ′, or the solid pattern printing layer 8 ′ and the pattern printing layer 8 and the surface protective layer 21 described above. It is possible to improve the adhesive strength by providing a primer layer or to protect the surface of the solid pattern printing layer 8 'and the pattern printing layer 8 to meet the high level requirements.

[0047] Further, the concavo-convex pattern 6 can be formed by heating press, hairline processing, or the like. The The patterns include, for example, conduit grooves, stone plate surface irregularities, cloth surface textures, satin texture, sand texture, hairlines, striated grooves, mirror surfaces, and the like.

[0048] It should be noted that the force described so far as the decorative material 2 provided with the surface protective layer 21 on the surface layer is not limited to this. For example, the decorative material 2 before forming the primer layer 5 and Z or the surface protective layer 21 in FIGS. 2 and 3 is placed on the hardness imparting layer 12 integrated with the plywood 11 via the adhesive layer 13. After the lamination, the primer layer 5 and Z 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. Although not shown, instead of the decorative material 2 shown in FIGS. 2 to 4, an oak, oak, sen, beech, etc. having a thickness of 0.15 to 0.7 mm, preferably 0.15 to 0.3 mm. Veneer veneers such as oysters and oaks may be used. In this case, as a matter of course, the surface protective layer 21 is provided after the protruding 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-described protruding plate is bonded to one surface of the polypropylene film, and embossing force is applied from the polypropylene film side. Then, a laminated material in which a surface protective layer made of curable resin is provided on the polypropylene film surface may be used. If a veneer is used, a non-woven fabric may be bonded to the back of the veneer (the surface on the plywood side) in consideration of dry crack prevention and workability!

Brief Description of Drawings

[0049] FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention.

FIG. 2 is a layer configuration diagram schematically showing a first embodiment of a decorative material having a surface protective layer on the surface layer constituting the floor material of the present invention.

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.

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.

Explanation of symbols

[0050] 1 Flooring 2 Decoration material

3, 13 Adhesive layer

5, 5, 5 "primer layer

6 Uneven pattern

7 Wiping ink

8 Pattern printing layer

8, Solid print layer

11 Plywood

12 Hardening layer

21 surface fefc layer

22 Transparent layer made of synthetic resin

22 'Synthetic resin sheet

23 Paper-based sheet

Fine particles

Next, the present invention will be described in more detail with reference to the following examples.

[0051] [Production of decorative material (decorative sheet) of second embodiment]

A solid print layer with a thickness of 3 m was formed on one side of a colored polypropylene film with a thickness of 60 μm that was subjected to double-sided corona discharge treatment with acrylic printing ink. On the solid pattern layer, a pattern printing layer composed of a grain pattern printing layer with a two-component curable urethane printing ink was formed by a gravure printing method. Thereafter, a urethane Z nitrified cotton primer layer was formed on the other surface by gravure printing. Next, after forming a 2 m-thick adhesive layer composed of a two-component curable urethane resin on the pattern printed layer surface, a benzotriazole-based UV absorber and a hindered amine radical scavenger were added to the adhesive layer surface. A polypropylene thermoplastic elastomer was heated and melt-extruded with a T-die extruder to form a transparent resin layer having a thickness of 80 m to produce an intermediate sheet.

[0052] After that, a concave portion was formed on the surface of the transparent resin layer with an embossed plate of wood grain conduit pattern. The concave portion is filled with acrylic monourethane resin (acrylic polyol is the main ingredient and isocyanate is added as a curing agent), and is dried by filling with sepia-colored wiping ink. A 2 m thick transparent primer layer was formed by applying a 2-component cured urethane-based resin with a Z urethane block copolymer as the main component and an isocyanate added as a curing agent. Next, the surface of the transparent primer layer is coated with urethane acrylate ionizing radiation curable resin, and irradiated with an electron beam (acceleration voltage: 175 KeV, irradiation amount: 5 Mrad) to obtain a transparent film with a thickness of 20 / zm. A decorative sheet having a surface protective layer was prepared.

Example 1

[0053] 11. A resin composition [wood flour (90% by weight, unsaturated polyester resin (manufactured by DH Material Co., Ltd.), chemically treated on the surface of an 8 mm thick plywood: Add 10 parts by weight of (Oligoester wood material) and 0.7 parts by weight of polymerization initiator (partial butyl peroxyisopropyl carbonate) to these total parts by weight. 200 g / m ^{2 was} applied. Thereafter, it was hot-pressed (temperature: 135 ° C, pressure: lkgZcm ² , time: 3 minutes) with a multi-stage press calorie 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 were sanded, an adhesive (made by Chuo Rika Kogyo Co., Ltd .: BA-10L (main agent) in 100 parts by weight BA-11B (curing agent) 2 . 5 parts by weight was blended] was applied in an amount of 80 gZm ² 'wet, and the decorative sheet was laminated on the coated surface. Then, the floor material was obtained by cold pressing (pressing time: 1 hour).

Example 2

[0054] A flooring was obtained in the same manner as in Example 1 except that 80 parts by weight of unsaturated polyester resin and 20 parts by weight of chemically treated wood flour were used as the composition of the resin composition.

Example 3

[0055] A flooring was obtained in the same manner as in Example 1 except that 75 parts by weight of unsaturated polyester resin and 25 parts by weight of chemically treated wood flour were used as the composition of the resin composition.

Example 4

[0056] A flooring was obtained in the same manner as in Example 1 except that the composition of the greave composition was 68 parts by weight of unsaturated polyester greaves and 32 parts by weight of chemically treated wood flour.

Example 5 [0057] A flooring was obtained in the same manner as in Example 1 except that 65 parts by weight of unsaturated polyester resin and 35 parts by weight of chemically treated wood flour were used as the composition of the resin composition.

Example 6

[0058] To the resin composition of Example 1, a polymerization accelerator (cobalt naphthenate "Co-NAPHTHEN ATE6% SHj, manufactured by Dainippon Ink and Chemicals, Inc.) A flooring material was prepared in the same manner as in Example 1 except that 0.5 part by weight was added to the total part by weight to prepare a resin composition, and the amount of the resin composition applied was 200 gZm ^2. Obtained.

[0059] Hereinafter, in Examples 7 to 12, the fiber length of wood flour is examined.

Example 7

[0060] 11. On the surface of an 8 mm thick plywood, 68 parts by weight of a resin composition [unsaturated polyester resin (manufactured by DH Material Co., Ltd.), chemically treated wood flour (manufactured by AGRIFU UTIYA CORPORATION]: 32 parts by weight of oligoesteri wood (wood material made from Chinese oak flour with a fiber length of 50 μm) and a polymerization initiator (partial butyl peroxyisopropyl carbonate) for these total parts by weight 0.7 part by weight added] was uniformly applied by a roll coating method at 200 g / m ² . Thereafter, hot pressing (temperature: 135 ° C, pressure: lkgZcm 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) is added to 100 parts by weight of BA-11B (curing agent) on the surface of the hardness imparting layer. 2. 5 parts by weight was mixed] with 80 gZm ² ′ wet, and the decorative sheet was laminated on the coated surface. Thereafter, cold pressing (pressing time: 1 hour) was performed to obtain a flooring. Example 8

[0061] Example 7 and Example 7 except that an oligoesterified wood material produced from Karabu wood flour having a fiber length of 60 μm manufactured by Agrifu Uchiya Kyoetsu Co., Ltd. was used as the chemically treated wood flour. A flooring was obtained in the same manner.

Example 9

[0062] As a wood powder that has been chemically treated, the fiber length made by AGRIFU YUTIYA CORPORATION is 1 A flooring was obtained in the same manner as in Example 7 except that the oligoester wood produced from 10 μm tang wood was used.

Example 10

[0063] Example 7 except that an oligoester wood material produced from Karagi wood flour having a fiber length of 150 μm manufactured by Agrifu Yuichi Itsuetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.

Example 11

[0064] Example 7 except that an oligoester wood material produced from Karabu wood flour having a fiber length of 200 μm manufactured by Agrifu Yuichi Kyoetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.

Example 12

[0065] Example 7 except that Oligoester wood wood material produced from Chinese wood flour with a fiber length of 2 10 μm manufactured by Agrifu Yuichi Itsuetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.

Example 13

[0066] A total of wood flour obtained by further subjecting the resin composition of Example 7 to a polymerization accelerator (cobalt naphthenate "Co-NAPHTHENA TE6% SHj manufactured by Dainippon Ink and Chemicals, Inc.) A flooring material was obtained in the same manner as in Example 7, except that 0.5 part by weight was added to the weight part to prepare a resin composition, and the amount of the resin composition applied was 200 gZm ^2. It was.

[0067] The flooring materials of Examples 1 to 13 produced above were subjected to a caster test (*: L), and their dent depths were measured and evaluated. The results are summarized in Table 1. . For reference, a caster test was conducted even on the single plywood used in this example, and the depth of the dent was measured.

[0068] [Table 1] Caster test results

Example 1

Example 2

Example 3

Example 4

Example 5 ©

Example 6

Example 7

Example 8

Example 9

Example 1 0 0

Example 1 1

Example 1 2 ○

Example 1 3 ○

[0069] * ii) Caster test:

Applying a load of 75 kg to a jig with three polyamide wheels (diameter: 75 mm, width: 25 mm) with a diameter of 260 mm and an interval of 120 degrees, the jig rotates in the direction of rotation every 5 minutes at a speed of 20 rpm. The test was performed at 1000 rpm, and the depth of the dents (unit: m) at that time was measured. The smaller the dent depth, the better the caster resistance. In addition, as evaluation criteria for caster resistance, our judgment criteria are X as a dent depth of 100 m or more as bad, ◯ as good when less than 100 m, and ◎ as best when a dent depth is less than 20 m. To do. 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.

[0070] As is clear from Table 1, the flooring materials of Examples 1 to 13 were more preferable for caster resistance than the plywood alone, and the results were as follows.

[0071] 2) Confirmation of surface smoothness:

By confirming the feel of the surface protective layer of the flooring materials of Examples 1 to 13, Examples 1 to 1

The surface smoothness of the flooring 3 was confirmed.

[0072] Examples 1 to: It was found that the flooring materials L 1 and 13 had excellent surface smoothness. Although the flooring material of Example 12 has a certain level of surface smoothness, the unevenness of the wood flour appears slightly on the surface of the decorative material (decorative sheet), so that the flooring material that requires surface smoothness is used. Is There may be some problems.

Claims

The scope of the claims

[I] A hardness imparting layer formed of a composition containing a 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 Floor material.

[2] The flooring material according to claim 1, wherein the chemically treated wood flour is fibrous and has a fiber length of 50 μm to 200 μm.

[3] The flooring according to claim 1, wherein the resin component is a thermosetting resin.

[4] In the hardness-imparting layer, the blending ratio of rosin and chemically treated wood flour is 65 to 90 parts by weight as rosin, and 35 to as chemically treated wood flour: L0 parts by weight, and the total amount is 100 weights 2. The flooring material according to claim 1, wherein the flooring material is formed from a composition formulated so as to be a part.

5. The flooring according to claim 1, wherein the decorative material is a decorative sheet including a synthetic resin sheet base material.

6. The flooring material according to claim 5, wherein the synthetic resin sheet base material comprises an olefin thermoplastic thermoplastic resin.

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

8. The flooring material according to claim 1, wherein the decorative material is a veneer.

[9] The flooring according to claim 1, wherein the decorative material includes a surface protective layer on a surface layer thereof.

10. The flooring according to claim 9, wherein the surface protective layer is made of ionizing radiation curable resin.

[II] The flooring according to claim 9, wherein the surface protective layer is a layer containing fine particles.