WO2007091614A1 - Materiau de revetement de sol - Google Patents

Materiau de revetement de sol Download PDF

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Publication number
WO2007091614A1
WO2007091614A1 PCT/JP2007/052153 JP2007052153W WO2007091614A1 WO 2007091614 A1 WO2007091614 A1 WO 2007091614A1 JP 2007052153 W JP2007052153 W JP 2007052153W WO 2007091614 A1 WO2007091614 A1 WO 2007091614A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
flooring
resin
decorative
wood flour
Prior art date
Application number
PCT/JP2007/052153
Other languages
English (en)
Japanese (ja)
Inventor
Hiroshi Matsubara
Isao Yoshimura
Original Assignee
Dai Nippon Printing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co., Ltd. filed Critical Dai Nippon Printing Co., Ltd.
Publication of WO2007091614A1 publication Critical patent/WO2007091614A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/02—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/042—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/06—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/0469—Ornamental plaques, e.g. decorative panels, decorative veneers comprising a decorative sheet and a core formed by one or more resin impregnated sheets of paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/026—Wood layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
    • E04F2290/04—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire
    • E04F2290/048—Specially adapted covering, lining or flooring elements not otherwise provided for for insulation or surface protection, e.g. against noise, impact or fire against static electricity

Definitions

  • 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.
  • 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.
  • a composite material in which a medium density fiberboard (MDF) is laminated on the surface of a plywood or a plywood is generally used.
  • MDF medium density fiberboard
  • 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.
  • Patent Document 1 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.
  • 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.
  • 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.
  • Patent Document 2 see, for example, Patent Document 2.
  • 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.
  • 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.
  • 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
  • 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
  • the present invention relates to the following flooring material.
  • 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.
  • 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.
  • the decorative material is a decorative sheet including a synthetic resin sheet base material.
  • the synthetic resin sheet substrate is made of an olefin thermoplastic thermoplastic resin.
  • 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.
  • the flooring of the present invention has excellent water resistance by adopting the above configuration.
  • 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).
  • FIG. 1 is a diagram schematically showing the basic layer structure of a flooring according to the present invention
  • 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
  • FIG. 4 is a floor material of the present invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • the hardness imparting layer 12 is mainly composed of rosin and chemically treated wood flour.
  • the resin any resin can be used as long as it can uniformly disperse and mix chemically treated wood flour.
  • 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
  • thermosetting (thermosetting) resin such as melamine resin, guanamine resin, melamine-urea co-condensed resin, silicon resin, polysiloxane resin.
  • thermoplastic 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.
  • thermoplastic resin It is preferable to use a mixture of more than one kind of thermosetting resin without any problems.
  • 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.
  • a curing agent such as a crosslinking agent and a polymerization initiator and a polymerization accelerator is added to the thermosetting resin.
  • 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.
  • 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.
  • 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.
  • 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 .
  • the fiber length of the wood flour is not particularly limited.
  • wood flour ( The fibers) are preferably entangled with each other. In view of this meaning, it is preferable that the fiber is long.
  • the fiber length of the wood flour is preferably 50 ⁇ m or more and 200 ⁇ m or less.
  • the fiber length can be measured, for example, by sieving wood flour.
  • 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.
  • 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! / ⁇ .
  • 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.
  • 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.
  • 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.
  • 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 ′.
  • 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 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.
  • Surface protective layer made of rosin 21 is formed.
  • 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.
  • 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 ⁇ -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.
  • 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 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • monomers, prepolymers or polymers are used singly or in combination.
  • 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.
  • Prepolymers having radically polymerizable unsaturated groups include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate. And polybulurpyrrolidone.
  • 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 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.
  • 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.
  • prepolymers such as ethers, urethane-based ethers, vinyl ether-based resins such as ester-based ethers, cyclic ether compounds, and spiro compounds.
  • 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) atare
  • Examples include (meth) attayllooxychetyl 2-hydroxypropyl phthalate, 2- (meth) attayloxypropyl hydrogen terephthalate, and the like.
  • 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.
  • the monomer having a cationic polymerizable functional group the monomer of a prepolymer having the cationic polymerizable functional group can be used.
  • a photopolymerization initiator is added as a sensitizer.
  • 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.
  • 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.
  • an inorganic substance and Z or an organic substance are contained.
  • inorganic substances include fine particles such as ⁇ -alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide.
  • 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.
  • 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.
  • 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.
  • 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 be a known organic ultraviolet absorber such as a benzotriazole, benzophenone, or triazine or a hindered amine, depending on the required physical properties.
  • 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.
  • 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 ′.
  • 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.
  • 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.
  • a chain extender such as diamine (component D) is added to the prepolymer to extend the chain.
  • 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.
  • Component A is a linear acrylate polymer having a hydroxyl group at the terminal.
  • 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.
  • 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.
  • the adhesion 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.
  • a polyester polyol having hydroxyl groups at both ends is used.
  • 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.
  • diol examples include ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol. And short chain diols such as 1,4-cyclohexanedimethanol and the like.
  • dibasic acid examples include adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
  • 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.
  • 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 '.
  • an acrylic polymer an acrylic resin component composed of components contributes to weather resistance and blocking resistance in the primer layer.
  • the molecular weight of component B is flexible in the primer layer.
  • polyester diol consisting of 3-methylpentanediol and 1,4-cyclohexanedimethanol 500 to 5000 (weight average molecular weight) is preferred.
  • the component C is an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule.
  • 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.
  • isophorone diisocyanate is preferable in terms of excellent physical properties and cost.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • aliphatic isocyanates are desirable for preventing thermal discoloration and weather resistance.
  • 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.
  • 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.
  • the concavo-convex pattern 6 can be formed by heating press, hairline processing, or the like.
  • 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.
  • 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.
  • 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.
  • the primer layer 5 and Z or the surface protective layer 21 may be provided.
  • 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.
  • 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.
  • the above-described protruding plate is bonded to one surface of the polypropylene film, and embossing force is applied from the polypropylene film side.
  • 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!
  • 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.
  • 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 ⁇ m that was subjected to double-sided corona discharge treatment with acrylic printing ink.
  • 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.
  • 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.
  • 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.
  • 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.
  • an electron beam acceleration voltage: 175 KeV, irradiation amount: 5 Mrad
  • 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.
  • 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).
  • 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.
  • 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.
  • 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 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 1 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.
  • a polymerization accelerator cobalt naphthenate "Co-NAPHTHEN ATE6% SHj, manufactured by Dainippon Ink and Chemicals, Inc.
  • Example 7 and Example 7 except that an oligoesterified wood material produced from Karabu wood flour having a fiber length of 60 ⁇ m manufactured by Agrifu Uchiya Kyoetsu Co., Ltd. was used as the chemically treated wood flour. A flooring was obtained in the same manner.
  • 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 ⁇ m tang wood was used.
  • Example 7 except that an oligoester wood material produced from Karagi wood flour having a fiber length of 150 ⁇ m manufactured by Agrifu Yuichi Itsuetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.
  • Example 7 except that an oligoester wood material produced from Karabu wood flour having a fiber length of 200 ⁇ m manufactured by Agrifu Yuichi Kyoetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.
  • Example 7 except that Oligoester wood wood material produced from Chinese wood flour with a fiber length of 2 10 ⁇ m manufactured by Agrifu Yuichi Itsuetsu Co., Ltd. was used as the chemically treated wood flour. In the same manner, a flooring was obtained.
  • 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.
  • 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.
  • 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.
  • 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.
  • the surface smoothness of the flooring 3 was confirmed.

Abstract

L'invention concerne un matériau de revêtement de sol ayant non seulement une résistance au défaut d'enfoncement et d'excellentes propriétés de résistance au frottement, de résistance à l'abrasion, de performance antitaches et de résistance à l'eau, mais se distinguant également particulièrement par sa surface lisse. L'invention concerne un matériau de revêtement de sol caractérisé en ce qu'une couche conférant de la dureté consistant en une composition contenant de la sciure de bois traitée avec un produit chimique et un composant à base de résine est apposée sur une surface principale de contreplaqué, et en ce que la couche conférant de la dureté est recouverte par le biais d'une couche adhésive avec un matériau décoratif.
PCT/JP2007/052153 2006-02-07 2007-02-07 Materiau de revetement de sol WO2007091614A1 (fr)

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JP2006-029306 2006-02-07
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009074251A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009074255A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009074249A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009097325A (ja) * 2007-09-28 2009-05-07 Dainippon Printing Co Ltd 床用化粧材
WO2009082099A1 (fr) * 2007-12-20 2009-07-02 Kwang Seok Oh Panneau de plancher
WO2014029887A1 (fr) * 2012-08-24 2014-02-27 Akzenta Paneele + Profile Gmbh Procédé d'impression sur un panneau mural ou de sol
WO2014060402A1 (fr) * 2012-10-17 2014-04-24 Akzenta Paneele + Profile Gmbh Procédé de fabrication d'un panneau mural ou de sol décoré
CN106351417A (zh) * 2016-08-27 2017-01-25 湖州展邦实业有限公司 一种防水耐磨地板及其制备方法
EP3063006A4 (fr) * 2013-11-01 2017-05-03 ZEP International Limited Panneau composite à base de polypropylène à impression numérique et revêtement de surface
EP3129228A4 (fr) * 2014-04-11 2017-12-27 Guangzhou Australian Eucalyptus Timber Flooring Co Ltd Procédé de fabrication d'un composite de bois d'oeuvre, composite de bois d'oeuvre obtenu et panneaux décoratifs comprenant un tel composite de bois d'oeuvre
US10538064B2 (en) 2014-04-11 2020-01-21 Guangzhou Austrailian Eucalyptus Timber Flooring Co Ltd. Method of manufacturing a timber composite, the timber composite obtained and decorative panels comprising such timber composite

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JPH063065B2 (ja) * 1987-05-25 1994-01-12 株式会社ノダ 床材及びその製造方法
JPH0596282U (ja) * 1992-06-05 1993-12-27 朝日ウッドテック株式会社 木質化粧材
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009074255A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009074249A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009074251A (ja) * 2007-09-19 2009-04-09 Dainippon Printing Co Ltd 床材
JP2009097325A (ja) * 2007-09-28 2009-05-07 Dainippon Printing Co Ltd 床用化粧材
WO2009082099A1 (fr) * 2007-12-20 2009-07-02 Kwang Seok Oh Panneau de plancher
CN103958213A (zh) * 2012-08-24 2014-07-30 阿卡曾塔板材型材有限公司 一种在墙或地板镶板上印刷的方法
WO2014029887A1 (fr) * 2012-08-24 2014-02-27 Akzenta Paneele + Profile Gmbh Procédé d'impression sur un panneau mural ou de sol
WO2014060402A1 (fr) * 2012-10-17 2014-04-24 Akzenta Paneele + Profile Gmbh Procédé de fabrication d'un panneau mural ou de sol décoré
EP3063006A4 (fr) * 2013-11-01 2017-05-03 ZEP International Limited Panneau composite à base de polypropylène à impression numérique et revêtement de surface
EP3129228A4 (fr) * 2014-04-11 2017-12-27 Guangzhou Australian Eucalyptus Timber Flooring Co Ltd Procédé de fabrication d'un composite de bois d'oeuvre, composite de bois d'oeuvre obtenu et panneaux décoratifs comprenant un tel composite de bois d'oeuvre
US10538064B2 (en) 2014-04-11 2020-01-21 Guangzhou Austrailian Eucalyptus Timber Flooring Co Ltd. Method of manufacturing a timber composite, the timber composite obtained and decorative panels comprising such timber composite
US11338557B2 (en) 2014-04-11 2022-05-24 Flooring Industries Limited, Sarl Method of manufacturing a timber composite, the timber composite obtained and decorative panels comprising such timber composite
US11701867B2 (en) 2014-04-11 2023-07-18 Flooring Industries Limited, Sarl Method of manufacturing a timber composite, the timber composite obtained and decorative panels comprising such timber composite
CN106351417A (zh) * 2016-08-27 2017-01-25 湖州展邦实业有限公司 一种防水耐磨地板及其制备方法

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