JP2006207343A - Floor material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a floor material hardly influenced by water and excellent not only in surface material property such as abrasion resistance and resistance to contamination but also in particularly fall impact resistance. <P>SOLUTION: The floor material 1 is formed by laminating an adhesive layer 3 and a decorative layer 2 in this order on a resin impregnated material cured layer surface of a composite material with a material cured layer 41 impregnated with a resin, laminated on one side of plywood 42, and providing a surface protective layer 21 formed of ionizing radiation cured resin, on the surface layer of the decorative layer 2. The material cured layer 41 impregnated with the resin is an integrally formed layer by thermocompression-bonding a material impregnated with thermosetting resin impregnated in glass paper with a basis weight of 30 g/m<SP>2</SP>or more, to one side of the plywood 42. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wood base material and a floor material provided with a decorative layer on the wood base material, and more particularly, a floor having excellent scratch resistance and contamination resistance, particularly caster resistance and drop impact resistance. It relates to materials.

  Conventionally, flooring materials in which a decorative sheet is attached to a wooden base material are known. As the decorative sheet, a surface protective layer made of a curable resin is usually provided on the surface in order to ensure surface physical properties required for a flooring material, that is, scratch resistance and stain resistance. In addition, as the wooden base material used for flooring, a plywood using Lauan material is usually used, but the flooring made of such a plywood is a caster part of furniture with casters, or a chair or When a load is applied to the tip of a leg of a desk or the like, the surface is easily scratched or dented, and the unevenness of the plywood surface appears on the surface of the decorative sheet as it is, and the design is likely to be impaired. (For example, refer to Patent Document 1).

Therefore, a floor material using a composite material in which a medium density fiberboard, so-called MDF is laminated, is adopted on the surface of the plywood on the side where the decorative sheet is pasted as a wooden base material. It was possible to solve the problem of flooring using a wood-based base material, but the flooring material composed of a composite base material using such a medium density fiberboard is much more than the flooring material composed of a single plywood. In addition to the high cost, the medium-density fiberboard swells by absorbing water, and the floor surface is likely to be wavy. Therefore, there is a problem that it is difficult to use on floors such as kitchens where water is easily scattered on the floor.
JP 2001-193267 A

  Therefore, the present invention has been made in view of the above problems, and it is needless to say that the first object of the present invention is hardly affected by water and is excellent in surface physical properties such as scratch resistance and contamination resistance. In particular, even when a load is applied to a caster or the like, that is, to provide a flooring material that is less likely to have scratches or dents on the surface in terms of caster resistance and that is excellent in drop impact resistance. A second object of the present invention is to provide a flooring material having an appearance with few irregularities and excellent smoothness.

In order to achieve the above object, the inventor of the present invention is characterized in that the present invention according to claim 1 includes an adhesive layer on the resin impregnated cured layer surface of a composite material in which a resin impregnated cured layer is laminated on one surface of a plywood. In a flooring in which decoration layers are sequentially laminated and a surface protective layer made of an ionizing radiation curable resin is provided on the surface of the decoration layer, the resin-impregnated material cured layer has a basis weight of 30 g / m ² or more. It is a layer integrally formed by thermocompression bonding a resin impregnated material obtained by impregnating paper with a thermosetting resin to one surface of the plywood.

  The present invention according to claim 2 is characterized in that, in the flooring according to claim 1, the cured resin impregnated layer comprises a plurality of layers.

  Further, the present invention according to claim 3 is characterized in that in the flooring according to any one of claims 1 and 2, the decorative layer is a decorative sheet made of a synthetic resin sheet base material. .

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

  Further, the present invention according to claim 5 is the flooring according to any one of claims 3 and 4, wherein the surface protective layer is a copolymer of acrylic resin and urethane resin and isocyanate on the synthetic resin sheet substrate. It is characterized by being formed through the primer layer formed from.

  Further, the present invention according to claim 6 is the flooring according to claim 3, wherein the decorative layer is formed by laminating a backer material on the surface of the decorative sheet made of the synthetic resin sheet base material on the adhesive layer side. It is characterized by being.

  The present invention according to claim 7 is the flooring according to any one of claims 1 and 2, characterized in that the decorative layer is a decorative sheet made of a paper-based sheet base material.

  The invention according to claim 8 is characterized in that, in the flooring according to any one of claims 1 to 7, the surface protective layer is a layer containing fine particles.

  The present invention according to claim 9 is characterized in that, in the flooring according to any one of claims 1 and 2, the decorative layer is a protruding plate.

  The present invention according to claim 10 is the flooring according to any one of claims 1 to 9, wherein the resin impregnated cured layer is laminated on the other surface of the plywood, The resin impregnated material impregnated with a curable resin is a layer integrally formed by thermocompression bonding to the other surface of the plywood. By configuring in this way, it is possible to prevent warping or twisting of the flooring material of the composite material during processing or over time.

In the flooring of the present invention, the resin impregnated cured layer is formed of a resin impregnated material obtained by impregnating a glass paper having a basis weight of 30 g / m ² or more with a thermosetting resin. In terms of caster resistance, etc., the surface is less likely to be scratched or dented, has excellent effects in terms of drop impact resistance, and has an excellent appearance with less unevenness and smoothness. In addition, by providing a surface protective layer made of an ionizing radiation curable resin on the surface of the decorative layer, an effect excellent in scratch resistance and contamination resistance is exhibited.

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention, and FIG. 2 is a diagram illustrating a first embodiment of a decorative layer 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 layer 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. Fig. 5 is a layer configuration diagram schematically showing a third embodiment of a decorative layer provided with a surface protective layer on the surface layer constituting Fig. 5, and Fig. 5 shows a decorative layer provided with a surface protective layer on the surface layer constituting the flooring of the present invention. 4 is a layer configuration diagram schematically showing an embodiment, in which 1 is a flooring, 2, 2 'is a decorative layer, 3, 3', 3 "are adhesive layers, 4 is a composite material, 5, 5 ', 5' is a primer layer, 6 is an uneven pattern, 7 is a wiping ink, 8 is a pattern printing layer, 8 'is a solid printing layer, 9 is a backer material, 21 is a surface protective layer, 22 is a synthetic resin A transparent sheet, 22 'is a synthetic resin sheet, 23 is a paper-based sheet, 41 is a resin-impregnated paper cured layer, 42 is a plywood, and α is a fine particle.

  FIG. 1 is a diagram schematically showing a basic layer structure of a flooring according to the present invention. The flooring 1 is the resin impregnation of a composite material 4 in which a cured resin impregnating layer 41 is laminated on a plywood 42. The decorative layer 2 having the surface protective layer 21 made of an ionizing radiation curable resin is provided on the material cured layer 41 via the adhesive layer 3. The cured resin impregnated layer 41 prevents the surface unevenness of the plywood 42 from appearing on the surface layer when the floor material 1 is used, and also provides a drop impact resistance and caster resistance when the floor material 1 is used. It is provided to improve the performance. As the plywood 42, for example, a plywood made of lauan material or pine material can be mentioned, and a single plate having a different fiber direction is arranged in a plurality of layers, for example, 3 layers, 5 layers, 7 layers. The surface fiber direction is configured in parallel with the longitudinal direction of the plywood, or the surface fiber direction is configured in a direction orthogonal to the longitudinal direction of the plywood. . Although not shown, a side part of the plywood 42 is provided with a real part composed of a female fruit and a male fruit, and the floor material 1 is formed by fitting the female fruit and the male fruit between the flooring materials 1 together. Laying on the floor.

As the resin impregnated material cured layer 41, a resin impregnated material obtained by impregnating glass paper with a thermosetting resin is used, and the resin impregnated material is placed on the plywood 42 and hot pressed to form the plywood. The composite material 4 integrated with 42 can be obtained. The hot pressing conditions vary depending on the thermosetting resin used, but are, for example, a temperature of 130 to 160 ° C., a pressure of 7 to 13 kg / cm ² , and a pressing time of about 20 to 120 seconds. Examples of the thermosetting resin include unsaturated polyester resin, one-pack or two-pack curable polyurethane resin, epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, and melamine-urea. Examples include co-condensation resins, silicon resins, polysiloxane resins, and the like, and one or more of these can be used in combination. The glass paper having a basis weight of 30 g / m ² or more as the base material impregnated with the thermosetting resin is preferably E glass fiber and contains 50% or more. The remainder may be any fiber that is compatible with papermaking, such as pulp fiber, and the larger the basis weight, the more preferable, but more preferably 50 g / m ² or more, and the cost and workability. Is 60 g / m ² or less. When the basis weight is less than 30 g / m ² , a sufficiently satisfactory effect in drop impact resistance cannot be obtained. Further, glass fibers having a thickness of 6 to 20 μm and consisting mainly of cut fibers having a length of 5 to 30 mm are suitable. When the thickness is less than 6 μm, the drop impact resistance is good. However, if the effect of using glass paper cannot be expected, and if it exceeds 20 μm, a further improvement effect in drop impact resistance cannot be expected, and it is better not to use it in consideration of cost. The length of the cut fiber is suitably 5 to 30 mm in consideration of papermaking properties. By using a glass paper having a basis weight of 30 g / m ² or more, preferably 50 g / m ² or more, composed of glass fibers mainly composed of cut fibers having the above thickness and length, the surface is excellent in drop impact resistance and surface. It can be used as a floor material with excellent smoothness. For example, when a glass cloth (glass woven fabric) having a thickness of 100 μm or more is used instead of glass paper, the texture appears on the surface. Therefore, it is not preferable in terms of design, and glass paper having a fiber thickness or basis weight in the above-described range is preferable. Further, as a method of impregnating glass paper with curable resin, liquefied thermosetting resin may be impregnated by well-known double-sided or single-sided application such as dipping method, roll coating method, gravure coating method and dried. Is. The application amount of the thermosetting resin in the wet state is approximately 50 to 300 g / m ² , preferably 70 to 250 g / m ² . Further, the glass paper may be treated with a known easy adhesion treatment agent such as a silane coupling agent or a titanium coupling agent as necessary.

  Further, the resin impregnated cured layer 41 may contain an inorganic filler as required. Examples of the inorganic filler include powdered aluminum oxide, silicon carbide, and carbon dioxide. Examples thereof include silicon, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, and gold sand.

Although not shown in the drawing, a composite material having a structure in which the resin impregnated cured layer 41 is provided on both surfaces of the plywood 42 may be used, and the composite material configured in this way is compared with the composite material 4. It is possible to prevent warping and twisting during processing, or warping and twisting of a flooring material for a composite material over time. The resin impregnated material cured layer 41 provided on the other surface of the plywood 42, that is, the surface opposite to the surface on which the decorative layer 2 is provided is warped or twisted during processing, or a flooring material. From the viewpoint of warping and twisting, it is preferable to form the same material as the resin impregnated cured layer 41 provided on the decorative layer 2 side. However, moisture penetration into the plywood 42 and moisture release from the plywood 42 are prevented. From the standpoint that it should be possible to prevent, the base material to be impregnated is not limited to glass paper, for example, paper base materials such as thin paper, kraft paper, titanium paper, cotton cloth, or woven or non-woven fabric made of various materials As the basis weight, approximately 30 to 120 g / m ² is appropriate, and the same resin as described above can be used as the thermosetting resin to be impregnated into the substrate. .

  Next, the said adhesive layer 3 which laminates | stacks the decoration layer 2 provided with the surface protection layer 21 which consists of ionizing radiation curable resin mentioned later and the said resin impregnated material cured layer 41 of the said composite material 4 is demonstrated. The adhesive layer 3 may be formed by a known dry lamination method using a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component. Examples of the polyol component include polyester polyol, polyester polyurethane polyol, polyether polyol, polyether polyurethane polyol, and the like. Examples of the isocyanate component include diisocyanates such as TDI, MDI, HDI, PIDI, and XDI, and starting materials thereof. In view of the coating amount, workability, and working environment, a moisture curable hot melt adhesive is preferable.

  The moisture-curing hot melt adhesive is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular ends, and is in the state of a thermoplastic resin that is solid at room temperature. Isocyanate groups react with each other by moisture in the air to cause chain extension reaction, resulting in a reaction product having a urea bond in the molecular chain, and the isocyanate group at the end of the molecule reacts with this urea bond, causing a burette bond. Branches and causes a crosslinking reaction. The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. Adhesive properties can be adjusted by appropriately employing one or more skeleton structures. In addition, when there is a urethane bond in the molecular chain, the terminal isocyanate group reacts with this urethane bond to produce an allophanate bond, and this allophanate bond also causes a crosslinking reaction.

  Specific examples of the polyisocyanate prepolymer include a urethane prepolymer having a polyurethane skeleton having an isocyanate group at a molecular terminal obtained by reacting an excess isocyanate with a polyol and having a urethane bond in the molecular chain. Further, as disclosed in JP-A No. 64-14287, a polyester skeleton and a polybutadiene skeleton obtained by adding a polyester polyol and a polyol having a polybutadiene skeleton to polyisocyanate in an arbitrary order and performing an addition reaction A crystalline urethane prepolymer having a structure in which is bonded by a urethane bond and having an isocyanate group at the molecular end, or a polycarbonate-based polyol and a polyisocyanate as disclosed in JP-A-2-305882 A polycarbonate urethane prepolymer having two or more isocyanate groups in the molecule obtained by reacting the polyester, and a polyester urethane having two or more isocyanate groups in the molecule obtained by reacting the polyester polyol and polyisocyanate. Emissions prepolymers, and the like.

  In addition to the above-mentioned various polyisocyanate prepolymers, the moisture-curable hot-melt adhesive includes, as necessary, the above-described essential reaction components, thermoplastic resins, and tackifiers. Various sub-materials such as plasticizers and fillers can also be added. Examples of these secondary materials include ethylene-vinyl acetate copolymer, low molecular weight polyethylene, modified polyolefin, atactic polypropylene, linear polyester, ethylene-ethyl acrylate (EAA), ethylene-methacrylate (EMA), 2-hydroxy. Thermoplastic resins such as ethyl methacrylate (HEMA), terpene-phenol resins, tackifiers such as rosin ester of abietic acid, fillers (external pigments) composed of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, coloring pigments , Curing catalyst, moisture remover, storage stabilizer, anti-aging agent and the like.

The coating amount of moisture-curable hot-melt adhesives described above are generally 20~90g / m ² as solids, preferably 40 to 60 g / m ^2. The adhesive application surface may be the surface opposite to the surface protective layer 21 of the decorative layer 2 or the resin impregnated material cured layer 41 surface.

  Next, the decoration layer 2 having the surface protective layer 21 made of ionizing radiation curable resin will be described. FIG. 2 is a layer configuration diagram schematically showing a first embodiment of a decorative layer provided with a surface protective layer on the surface layer constituting the flooring of the present invention. The decorative layer 2 is a synthetic resin sheet base material. After embossing on one surface of the synthetic resin transparent sheet 22 to provide a concavo-convex pattern 6, wiping treatment is performed on the surface to fill the concave portion of the concavo-convex pattern 6 with the wiping ink 7, and then the entire exposed surface A makeup comprising a synthetic resin sheet base material in which a primer layer 5 is provided and a pattern printing layer 8 and a solid pattern printing layer 8 ′ are sequentially printed on the other surface of the synthetic resin transparent sheet 22 via a primer layer 5 ′. A surface protection layer 21 made of an ionizing radiation curable resin is formed on the primer layer 5 of the decorative sheet. In the decorative layer 2, the solid pattern printing layer 82 of the decorative layer 2 and the resin impregnated cured layer 41 of the composite material 4 are bonded via the adhesive layer 3.

  FIG. 3 is a layer configuration diagram schematically showing a second embodiment of a decorative layer having a surface protective layer on the surface layer constituting the flooring of the present invention. The decorative layer 2 is a synthetic resin sheet base material. A primer layer 5 ″ is provided on at least one surface of the synthetic resin sheet 22 ′, and a solid pattern printing layer 8 ′ and a pattern printing layer 8 are sequentially printed on the primer layer 5 ″, and further on the pattern printing layer 8 side. The synthetic resin transparent sheet 22 is well-known dry lamination via the adhesive layer 3 ′ formed of a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component, as described in the adhesive layer 3. The surface of the synthetic resin transparent sheet 22 is embossed to provide a concavo-convex pattern 6, and then, as shown in FIG. Pattern 6 A decorative sheet made of a synthetic resin sheet base material filled with wiping ink 7 in the inside and further provided with a primer layer 5 on the surface, the surface made of ionizing radiation curable resin on the primer layer 5 of the decorative sheet The protective layer 21 is formed. In the decorative layer 2, the synthetic resin sheet 22 ′ of the decorative layer 2 and the resin impregnated cured layer 41 of the composite material 4 are bonded via the adhesive layer 3. The synthetic resin sheet 22 'is generally a colored sheet, but may be a non-colored sheet. In addition, although the decoration layer 2 shown in FIGS. 2 and 3 showed the embodiment which carried out embossing and the wiping process, the decoration layer 2 used for this invention is not restricted to this, The mirror surface finish excellent in surface smoothness It may be a decorative layer.

  FIG. 4 is a layer configuration diagram schematically showing a third embodiment of a decorative layer provided with a surface protective layer on the surface layer constituting the flooring of the present invention, wherein the decorative layer 2 is paper as a paper-based sheet substrate. A decorative sheet made of a paper-based sheet base material in which a solid pattern printing layer 8 ′ and a pattern printing layer 8 are sequentially printed on one side of the pattern sheet 23, and fine particles α are applied to the entire surface on the pattern printing layer 8 side. The surface protective layer 21 made of the ionizing radiation curable resin contained is formed. In the decorative layer 2, the paper-based sheet 23 of the decorative layer 2 and the resin-impregnated cured layer 41 of the composite material 4 are bonded via the adhesive layer 3.

  Next, various materials constituting the decorative layer 2 will be described. First, as the synthetic resin-made transparent sheet 22 and the synthetic resin-made sheet 22 ′, because they are excellent in processability and do not generate harmful gases during combustion, saturated polyester resins and low-density polyethylene (linear low-density polyethylene). Medium density polyethylene, high density polyethylene, homopolypropylene, ethylene α-olefin copolymer, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, An olefinic thermoplastic resin such as a saponified ethylene-vinyl acetate copolymer or a mixture thereof can be mentioned, but the olefinic thermoplastic resin is preferred in view of its relatively low cost. The synthetic resin transparent sheet 22 and the synthetic resin sheet 22 ′ may be in an unstretched state or a stretched state in a uniaxial or biaxial direction. It is about 60 to 300 μm. In addition, these sheets may be subjected to well-known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on necessary surfaces as necessary.

  Examples of the paper-based sheet 23 include thin paper, craft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like. Examples thereof include glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, carbon fibers and other inorganic fibers, polyester, vinylon and other woven or non-woven fabrics. However, it is better not to use a woven fabric from the viewpoint of design because the texture appears on the surface.

  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, or a silk screen printing method. Examples of the pattern print layer 8 include a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, a character, a symbol, a line drawing, and various abstract pattern patterns. As the solid pattern print layer 8 ′, Solid printed with colored ink having concealability. 2 to 4 show the configuration in which both the pattern print layer 8 and the solid pattern print layer 8 ′ are provided, any one of the configurations may be used.

  Examples of the ink for forming the pattern print layer 8 and the solid pattern print layer 8 ′ include chlorinated polyethylene such as chlorinated polyethylene and chlorinated polypropylene as a vehicle, polyester, polyurethane composed of isocyanate and polyol, polyacryl, Polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin, etc. are used in a mixture of one or more, and pigments, solvents, various auxiliary agents, etc. are added to the ink. In consideration of environmental problems, non-chlorine mixed with one or more of polyester, polyurethane consisting of isocyanate and polyol, polyacryl, polyvinyl acetate, cellulose resin, polyamide resin, etc. System vehicles are suitable, more preferably poly Ester, polyurethane consisting of isocyanate and polyol, polyacrylic, is a mixture one or two or more kinds of such polyamide-based resin. The above-described ink may be used for the wiping ink 7 as well.

  Next, the ionizing radiation curable resin for forming the surface protective layer 21 will be described. As the ionizing radiation curable resin, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as epoxy group in the molecule, It consists of a polymer or polymer. These monomers, prepolymers or polymers are used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and is usually an ultraviolet ray or an electron beam.

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

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

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

  In addition, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene 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, tri Propylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyloxy Examples thereof include ethyl phosphate.

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

When the above-mentioned ionizing radiation curable resin is cured by irradiating with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. In the case of a resin system having a radical polymerizable unsaturated group, photoinitiators include acetophenones, benzophenones, thioxanthones, benzoin, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a freeroxyxonium diallyl iodosyl salt, etc. should be used alone or as a mixture. Can do. In addition, generally the addition amount of these photoinitiators is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins. As the method for forming the surface protective layer 21, the above-mentioned ionizing radiation curable resin is made into a solution, and the synthetic resin transparent sheet 22 or the paper-based substrate 23 is formed by a known coating method such as a gravure coating method or a roll coating method. It can form by apply | coating to the predetermined surface. As a coating amount, about 5-200 g / m < ² > is suitable in general as solid content, Preferably it is 15-30 g / m < ² >.

  Next, when the surface protective layer 21 made of an ionizing radiation curable resin is provided with one layer of scratch resistance and wear resistance, aluminum oxide, silicon carbide, silicon dioxide, calcium titanate, barium titanate, Fine particles such as magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, gold sand, graphite and other organic particles such as beads made of synthetic resin such as crosslinked acrylic This can be achieved by adding α (see FIG. 4). The fine particles α (see FIG. 4) may have protrusions or corners on the surface of the fine particles. However, a spherical shape, no ellipse, or a shape close to these without protrusions or corners is suitable for processing, and a shoe sole. It is preferable from the viewpoint of not wearing the like. The average particle diameter of the fine particles α needs to be selected and used depending on the coating thickness of the surface protective layer 21, but basically the fine particles α are partially exposed from the surface protective layer 21. Usually, the average particle size is about 5 to 100 μm. Further, the ratio of the fine particles α to 100 parts by weight of the ionizing radiation curable resin is 1 to 50 parts by weight, preferably 5 to 20 parts by weight. In the examples, the fine particles α are included only in the surface protective layer 21 of the decorative layer 2 of the third embodiment shown in FIG. 4, but the first embodiment of FIGS. It may be contained in the surface protective layer 21 of the decorative layer 2 of the second embodiment.

  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 sheet 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 sheet 22, the pattern printing layer 8 and the solid pattern printing layer 8 ′, and the primer layer 5 ″ is made of the synthetic resin. It is provided for the purpose of improving the adhesive strength between the sheet 22 ′ and the solid print layer 8 ′. Hereinafter, the primer layers 5, 5 ′, and 5 ″ are collectively referred to as a primer layer. The primer layer includes (i) a copolymer of an acrylic resin and a urethane resin, and (ii) an isocyanate. That is, the copolymer of the acrylic resin and the urethane resin (i) is 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), a diisocyanate component (Component C) mixed and reacted to form a prepolymer, and a chain extender (Component D) such as diamine is further added to the prepolymer to extend the chain. As a result of this reaction, a polyester urethane is formed, an acrylic polymer component is introduced into the molecule, and an acrylic polymer having a hydroxyl group at the end is introduced. Ester urethane copolymer is formed this acryl -. Those cured by reaction with an isocyanate of the hydroxyl end of the polyesterurethane copolymer (ii) is the primer layer.

  As the component A, a linear acrylate polymer having a hydroxyl group at the terminal is used. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferable because it is excellent in weather resistance (particularly the property against photodegradation) and can be easily copolymerized with urethane. . The component A is an acrylic resin component in the copolymer, and those having a molecular weight of 5000 to 7000 (weight average molecular weight) are preferably used because of particularly good weather resistance and adhesiveness. In addition, the component A may be used only having a hydroxyl group at both ends, but a mixture having a conjugated double bond at one end is mixed with the above-mentioned one having a hydroxyl group at both ends. Is also good. By mixing the acrylic polymer in which the conjugated double bond remains, the conjugated double bond of the layer contacting the primer layer, for example, the ionizing radiation curable resin of the surface protective layer 21 and the acrylic polymer reacts. In addition, 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. The component B is a polyester diol having hydroxyl groups at both ends. Examples of the polyester diol include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. Examples thereof include a derived polyester compound. Examples of the diol include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol, and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. Preferred as the polyester polyol is adipate-based polyester using adipic acid or a mixture of adipic acid and terephthalic acid as the acid component, particularly preferably adipic acid, and 3-methylpentanediol and 1,4-cyclohexanedimethanol as the diol component. is there.

  In the primer layer, the urethane resin component formed by the reaction of the component B and the component C gives the primer layer flexibility, and the synthetic resin transparent sheet 22 or the synthetic resin sheet 22 ′ Contributes to the adhesion of Moreover, the acrylic resin component which consists of an acrylic polymer contributes to a weather resistance and blocking resistance in the said primer layer. In the urethane resin, the molecular weight of the component B may be within a range in which a urethane resin capable of sufficiently exhibiting flexibility in the primer layer is obtained. Adipic acid or a mixture of adipic acid and terephthalic acid, and 3-methylpentanediol In the case of a polyester diol composed of 1,4-cyclohexanedimethanol, 500 to 5000 (weight average molecular weight) is preferable.

  As the component C, an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule is used. As this diisocyanate, for example, tetra-ethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4′- Examples thereof include 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 and the isocyanate group is such that the isocyanate group becomes excessive. To.

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

Addition of isocyanate of (ii) to acrylic-polyester urethane copolymer of (i), coating method, coating solution adjusted to necessary viscosity in consideration of coating amount after drying, gravure coating method, roll The primer layer can be formed by coating by a known coating method such as a coating method. The coating amount after drying of the primer layer is from 1 to 20 g / m ^2, preferably from 1 to 5 g / m ^2. The primer layer may be a layer to which an additive such as a filler such as silica powder, a light stabilizer, or a colorant is added as necessary. The isocyanate of (ii) is not limited as long as it can be crosslinked and cured by reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (i). An aliphatic isocyanate can be used, and an aliphatic isocyanate is particularly desirable from the viewpoint of thermal discoloration prevention and weather resistance. Specifically, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate monomer, or a multimer such as dimer or trimer thereof, or And polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols. In addition, in the decoration layer 2 of FIG. 2, FIG. 3, although the thing of the structure which provided the primer layer (The layer shown by the code | symbol 5, 5 ', 5''on FIG. 2, 3) was shown, It is a specification that meets the high level requirements for flooring, and when the required level for flooring is low, these primer layers (layers indicated by reference numerals 5, 5 ′, 5 ″ on FIGS. 2 and 3) are necessarily used. Further, in FIG. 4, between the paper-based sheet 23 and the solid pattern printing layer 8 ′, or between the solid pattern printing layer 8 ′ and the pattern printing layer 8 and the surface protection. Specifications that meet the high level requirements by providing the above-mentioned primer layer between the layer 21 and improving the adhesive strength, or by protecting the surface of the solid print layer 8 ′ and the pattern print layer 8 It is good.

  Moreover, the said uneven | corrugated pattern 6 can be formed by heating press, a hairline process, etc., As the pattern, for example, a conduit groove | channel, a stone plate surface unevenness | corrugation, a cloth surface texture, a satin texture, a sand texture, a hairline, a multiline groove | channel, Mirror surface etc.

  FIG. 5 is a layer configuration diagram schematically showing a fourth embodiment of the decorative layer having a surface protective layer on the surface layer constituting the flooring of the present invention, and the decorative layer 2 ′ is shown in FIG. A backer material 9 is laminated on the surface of the synthetic resin sheet 22 ′ of the decorative layer 2 of the second embodiment via an adhesive layer 3 ″ made of the same resin as the adhesive layer 3 described above. Otherwise, this embodiment is the same as the second embodiment shown in Fig. 3. In this case, although not shown, the decoration layer 2 'is used instead of the decoration layer 2 shown in Fig. 1, The backer material 9 of the decorative layer 2 ′ and the resin impregnated cured layer 41 of the composite material 4 are bonded together via the adhesive layer 3 to form the flooring 1. As the backer material 9, In view of recent environmental problems, resins that do not contain halogen elements in their molecular structure are suitable. It consists of resins such as ethylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate-isophthalate copolymer, polyimide, polystyrene, polyamide, and ABS. Sheet, crystalline polyethylene terephthalate sheet (so-called C-PET), amorphous polyethylene terephthalate sheet (so-called A-PET), or highly heat-resistant polyalkylene terephthalate sheet [so-called PET-G manufactured by Eastman Chemical Company (Trade name)] and the like, and a thickness of about 200 to 500 [mu] m is appropriate as the thickness, These sheets may be a single layer or multiple layers. The resin to be used may be a single resin or a mixture, and the backer material 9 may be provided on a necessary surface such as corona discharge treatment, ozone treatment, plasma treatment, etc. Although not shown, the backer material 9 may be applied to the back surface (opposite surface of the surface protective layer 21) of the decorative layer 2 of the first embodiment shown in FIG. It ’s good.

  Heretofore, the description has been made with the decorative layers 2 and 2 'having the surface protective layer 21 provided on the surface layer, but the flooring of the present invention is not limited to this, for example, FIGS. The primer layer 5 and / or the surface protective layer 21 before forming the primer layer 5 and / or the surface protective layer 21 are laminated on the composite material 4 and then the primer layer 5 and / or the surface protective layer 21 are provided. Alternatively, the surface protective layer 21 may be provided after the decoration layer 2 before forming the surface protective layer 21 in FIG. 4 is laminated on the composite material 4. . In addition, although not shown, instead of the decorative layers 2 and 2 ′ shown in FIGS. 2 to 5, an oak, oak, or center having a thickness of 0.15 to 0.7 mm, preferably 0.15 to 0.3 mm. A protruding plate such as beech, zelkova or oak may be used. In this case, as a matter of course, the surface protective layer 21 is provided after the projecting plate is laminated on the composite material 4. Although not shown, instead of the decorative layers 2 and 2 ′ shown in FIGS. 2 to 5, the above-mentioned projecting plate is bonded to one surface of the polypropylene film, and then embossed from the polypropylene film side, Thereafter, a laminated material in which a surface protective layer made of an ionizing radiation curable resin is provided on the polypropylene film surface may be used. In the specification using a veneer, paper or non-woven fabric may be bonded to the back surface (surface on the plywood side) of the veneer in consideration of prevention of dry cracking and workability.

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

[Production of first composite material]
Glass paper having a basis weight of 60 g / m ² [manufactured by Oji Paper Co., Ltd .: GHN-00-060 (GC) L (trade name)] was added to 100 parts by weight of impregnating resin (unsaturated polyester resin / diallyl phthalate resin = 80/20). In contrast, a resin impregnated material impregnated with 242 g / m ² of resin in a wet state by dipping in an impregnated resin solution containing 67 parts by weight of a mixed solvent of three types (acetone / butanol / pentanol) A resin-impregnated material impregnated with 22 g / m ² ) was prepared. Next, the resin impregnated material prepared above was placed on one surface of a lauan plywood (5ply) adjusted to a thickness of 11.7 mm, and hot pressing (conditions: 145 ° C., 8 kg / cm ² , 1 And a first composite material having a resin impregnated cured layer on one side was prepared.

[Production of second composite material]
A second composite material is produced in the same manner as the first composite material, except that the basis weight of the glass paper is 50 g / m ² [Oji Paper: GHN-00-050 (GC) L (trade name)]. did.

[Production of third composite material]
A third composite material was produced in the same manner as the first composite material, except that the basis weight of the glass paper was 30 g / m ² [Oji Paper Co., Ltd .: GHN-00-030 (GC) L (trade name)]. did.

[Fabrication of fourth composite material]
A fourth composite material was produced in the same manner as the first composite material except that kraft paper having a basis weight of 60 g / m ² was used instead of glass paper.

[Fifth composite material production]
A fifth composite material was produced in the same manner as the first composite material except that a polyester nonwoven fabric having a basis weight of 60 g / m ² was used instead of the glass paper.

[Preparation of a decorative layer (a decorative sheet of the first embodiment) provided with the surface protective layer of the first embodiment]
An acrylic-urethane resin (hexamethylene on 100 parts by weight of acrylic polyol) on one side (back side) of a 120 μm-thick polypropylene film (manufactured by Mitsubishi Chemical MKV Co., Ltd .: 150AG3 (trade name)) subjected to corona discharge treatment on both sides A resin containing 5 parts by weight of diisocyanate) is applied by gravure printing so that the solid content is 2 g / m ² to form a printing primer layer, and an acrylic-urethane resin (acrylic) is formed on the printing primer layer. Using a printing ink made of a resin in which 5 parts by weight of hexamethylene diisocyanate was added to 100 parts by weight of polyol, a woodgrain pattern printing layer and a solid pattern printing layer were formed by gravure printing. Thereafter, a concave portion is provided with an embossed plate on the other surface (front surface) of the polypropylene film so as to correspond to the conduit portion of the wood grain pattern printed layer, and an acrylic-urethane resin (acrylic polyol 100 parts by weight) is formed in the concave portion. A sepia-colored wiping ink comprising 5 parts by weight of hexamethylene diisocyanate) is filled and dried, and an acrylic-urethane resin (a resin in which 5 parts by weight of hexamethylene diisocyanate is added to 100 parts by weight of acrylic polyol). ) The solution is applied by gravure printing so that the solid content is 2 g / m ² to form a primer layer for the surface protective layer, and then ionizing radiation curable resin [large Nissei Kagaku Kogyo Co., Ltd .: EBF-04 (trade name)] was applied and dried by a roll coating method, and then Line (175KeV, 5Mrad) solids by irradiating it to prepare a decorative layer having a surface protective layer of the first embodiment to form a surface protective layer of 20 g / m ² (decorative sheet of the first embodiment).

A moisture curable hot melt adhesive [manufactured by Hitachi Chemical Co., Ltd .: Hibon YR010-8L (trade name)] is applied to the surface of the resin impregnated material curing agent layer of the first composite material prepared above by a roll coating method. The flooring of the present invention was obtained by applying m ² and laminating the decorative sheet of the first embodiment produced above so that the surface protective layer 21 was exposed.

  A flooring of the present invention was obtained in the same manner as in Example 1 except that the second composite material was used instead of the first composite material.

  A flooring of the present invention was obtained in the same manner as in Example 1 except that the third composite material was used instead of the first composite material.

[Comparative Example 1]
A flooring as a comparative example was obtained in the same manner as in Example 1 except that the fourth composite material was used instead of the first composite material.

[Comparative Example 2]
A flooring as a comparative example was obtained in the same manner as in Example 1 except that the fifth composite material was used instead of the first composite material.

  With respect to the floor materials of Examples 1 to 3 and Comparative Examples 1 and 2 prepared above, the drop impact resistance was evaluated by the evaluation method described below, and the results are shown in Table 1. In addition, as an evaluation method of the drop impact resistance, a DuPont impact test (weight: 500 g, drop height: 300 mm, striking diameter R: 6.3 mm) is performed from the decorative sheet side, and the depth of the floor material dent at that time (Unit: μm) was measured. The smaller the dent depth, the better the drop impact resistance. For reference, the drop impact resistance of the lauan plywood used at that time was also evaluated.

  As is clear from Table 1, the flooring materials of Examples 1 to 3 are superior in drop impact resistance compared to the flooring materials of Comparative Examples 1 and 2, and the flooring materials of Examples 1 and 2 are particularly Comparative Example 1. It was possible to have a drop impact resistance that was significantly superior to that of No. 2 flooring. The caster resistance was a result of the same tendency as the drop impact resistance, so evaluation was omitted.

It is a figure showing the basic layer composition of the flooring concerning the present invention diagrammatically. BRIEF DESCRIPTION OF THE DRAWINGS It is a layer block diagram which shows 1st Embodiment of the decoration layer provided with the surface protection layer in the surface layer which comprises the flooring of this invention schematically. It is a layer block diagram which shows schematically 2nd Embodiment of the decoration layer provided with the surface protection layer in the surface layer which comprises the flooring of this invention. It is a layer block diagram which shows schematically 3rd Embodiment of the decoration layer provided with the surface protection layer in the surface layer which comprises the flooring of this invention. It is a layer block diagram which shows diagrammatically 4th Embodiment of the decoration layer provided with the surface protection layer in the surface layer which comprises the flooring of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flooring material 2,2 'Decoration layer 3,3', 3 "Adhesive layer 4 Composite material 5,5 ', 5" Primer layer 6 Uneven pattern 7 Wiping ink 8 Picture printing layer 8' Solid printing layer 9 Backer material DESCRIPTION OF SYMBOLS 21 Surface protective layer 22 Synthetic resin transparent sheet 22 'Synthetic resin sheet 23 Paper-based sheet 41 Resin impregnated paper hardened layer 42 Plywood α Fine particles

Claims (10)

An adhesive layer and a decorative layer are sequentially laminated on the surface of the resin impregnated material cured layer of the composite material in which a resin impregnated material cured layer is laminated on one surface of the plywood, and a surface made of an ionizing radiation curable resin on the surface layer of the decorative layer In a flooring provided with a protective layer, a resin impregnated material obtained by impregnating a glass paper having a basis weight of 30 g / m ² or more with a thermosetting resin into the resin impregnated material cured layer is heated on one surface of the plywood. A flooring material characterized by being a layer integrally formed by pressure bonding. 2. The flooring according to claim 1, wherein the cured resin impregnated layer is composed of a plurality of layers. The flooring according to claim 1, wherein the decorative layer is a decorative sheet made of a synthetic resin sheet base material. The floor material according to claim 3, wherein the synthetic resin sheet base material is made of an olefin-based thermoplastic resin. The said surface protective layer is formed in the said synthetic resin sheet base material through the primer layer formed from the copolymer of an acrylic resin and a urethane resin, and isocyanate. Crab flooring. The flooring material according to claim 3, wherein the decorative layer is formed by laminating a backer material on a surface of the decorative sheet made of the synthetic resin sheet base material on the adhesive layer side. The flooring according to claim 1, wherein the decorative layer is a decorative sheet made of a paper-based sheet base material. The floor covering according to any one of claims 1 to 7, wherein the surface protective layer is a layer containing fine particles. The flooring according to any one of claims 1 and 2, wherein the decorative layer is a veneer. A resin impregnated cured layer was laminated on the other side of the plywood, and the resin impregnated cured layer impregnated with a curable resin was thermocompression-bonded to the other side of the plywood and integrally molded. It is a layer, The flooring in any one of Claims 1-9 characterized by the above-mentioned.

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