JP2008082119A - Flooring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide flooring which is hardly affected by water and excellent in surface property such as scratch resistance, stain resistance and hardly scratched or dented on a surface even if a load is applied to a caster or the like or a falling impact is applied to the flooring. <P>SOLUTION: Resin impregnation paper impregnated with a diallyl phthalate resin is placed on one surface of plywood, and the resin impregnation paper is hardened by hot-press molding to form a hard layer of the resin impregnation paper integrated with the plywood. The flooring is formed of a decorative sheet having a surface protective layer formed of an ionizing radiation hardening type resin which is laminated on the surface layer of the hard layer of the resin impregnation paper through an adhesive layer. The flooring includes an impregnation substrate used in the resin impregnation paper which is not less than 140 g/m<SP>2</SP>and not more than 200 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a wood base material and a flooring material in which a decorative sheet is attached to the wood base material. More specifically, the invention is excellent in scratch resistance and stain resistance, particularly caster resistance and drop impact resistance. It relates to flooring.

  Conventionally, flooring materials in which a decorative sheet is attached to a wooden base material are known. As the decorative sheet used for the flooring, a surface protective layer made of a curable resin is usually provided on the surface from the viewpoint of ensuring the surface properties required for the flooring, that is, scratch resistance and contamination resistance. Yes. 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).

  As a woody base material that solves the above problems, a flooring using a composite material in which a medium density fiberboard, so-called MDF, is laminated on the surface of the plywood on which the decorative sheet is pasted has come to be adopted. . However, the floor material made of a composite material using such a medium density fiber board is more expensive than the floor material made of a single plywood, and the medium density fiber board swells by absorbing water. Since the surface is easily wavy, there is a problem that it is difficult to use on the floor of a kitchen or the like where water is easily scattered on the floor.

  The present applicant has previously proposed a flooring that is resistant to water so that it can be applied to floors of kitchens and the like where water is easily scattered (see, for example, Patent Document 2). The invention described in Patent Document 2 uses a composite material in which resin-impregnated paper impregnated with diallyl phthalate resin is impregnated on a plywood and is integrated by hot pressing, and this is used as a substrate. Is a flooring laminated with a decorative sheet having a surface protective layer made of an ionizing radiation curable resin through an adhesive layer, and has excellent physical properties such as water resistance, scratch resistance and stain resistance, caster resistance and resistance. Although it could be excellent in terms of drop impact, for example, plywood using a veneer (small-diameter wood veneer) connected to the surface layer, a plywood made of afforestation material (early timber), or softwood plywood, etc. In plywood with a poor surface condition, surface defects such as base material duck, base material surface knots or cracks, or surface irregularities may appear on the surface of the decorative sheet, which may reduce the design properties. As a problem of dropping the value of Can not be erased, this solution has been desired.

Therefore, as a result of various researches, by using an impregnated base material with increased basis weight, even for plywood with a poor surface condition, such as base material duck, base material surface nodes and cracks, surface irregularities, etc. It has been found that the surface of the decorative sheet can be made excellent in smoothness because it is hardly affected by surface defects, and further, caster resistance and drop impact resistance can be improved. The present invention has been completed.
JP 2001-193267 A JP 2006-46053 A

  Therefore, the present invention is not easily affected by water and has excellent surface properties such as scratch resistance and contamination resistance, as well as when a load is applied to a caster (caster resistance) or when a drop impact is applied. Also in (drop impact resistance), it is to provide a flooring which is hard to be scratched or dented on the surface. Moreover, this invention is providing the flooring which is excellent in surface smoothness also with respect to the plywood with a bad surface state.

In order to achieve the above-mentioned object, the inventor of the present invention described in claim 1 is characterized in that a resin-impregnated paper impregnated with diallyl phthalate resin is placed on one surface of a plywood, and the resin is subjected to hot pressing. A decorative sheet comprising a resin-impregnated paper cured layer integrated with the plywood by curing the impregnated paper, and having a surface protective layer made of an ionizing radiation curable resin on the surface layer through an adhesive layer on the resin-impregnated paper cured layer surface In the flooring laminated with the above, the impregnated base material used for the resin-impregnated paper is 140 g / m ² or more and 200 g / m ² or less.

  According to a second aspect of the present invention, in the flooring according to the first aspect, the decorative sheet is made of a synthetic resin sheet base material.

  According to a third aspect of the present invention, in the flooring according to the second aspect, the synthetic resin sheet base material is made of an olefin-based thermoplastic resin.

  Further, the present invention according to claim 4 is the flooring according to any one of claims 2 and 3, 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.

  The present invention according to claim 5 is characterized in that, in the floor material according to claim 2, a backer material is laminated on the surface of the synthetic resin sheet base material on the side of the adhesive layer. is there.

  According to a sixth aspect of the present invention, in the flooring according to the first aspect, the decorative sheet is made of a paper-based sheet base material.

  The present invention according to claim 7 is the flooring according to any one of claims 1 to 6, wherein the surface protective layer is a layer containing fine particles.

  The present invention according to claim 8 is the flooring according to claim 1, wherein at least a surface layer of the plywood is any one of a veneer made of a small diameter tree, a veneer made of a plantation material, and a veneer made of a conifer. It is a characteristic.

  The present invention according to claim 9 is the floor material according to any one of claims 1 to 8, wherein a resin-impregnated paper impregnated with diallyl phthalate resin is placed on the other surface of the plywood, A resin-impregnated paper cured layer integrated with the plywood by molding and curing the resin-impregnated paper is provided. 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.

  The flooring of the present invention does not swell even when water permeates, has excellent scratch resistance and contamination resistance, and also has excellent effects in caster resistance and drop impact resistance. Even when a plywood having a poor surface condition is used as the woody base material, the flooring material has an excellent effect that it can be a flooring material having excellent surface smoothness.

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram schematically showing a basic layer configuration of a flooring according to the present invention. FIG. 2 is a layer configuration diagram schematically showing a first embodiment of a decorative sheet constituting the flooring of the present invention. 3 is a layer configuration diagram schematically showing a second embodiment of the decorative sheet constituting the flooring material of the present invention, and FIG. 4 is a layer schematically showing the third embodiment of the decorative sheet constituting the flooring material of the present invention. FIG. 5 is a layer configuration diagram schematically showing a fourth embodiment of a decorative sheet constituting the flooring of the present invention, in which 1 is a flooring, 2, 2 ′ are decorative sheets, 3, 3 ', 3 "is an adhesive layer, 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 pattern printing layer, 9 is a backer material, 21 is a surface protection layer, 22 is a synthetic resin transparent sheet, 22 'is a synthetic resin sheet, 23 is a paper-based sheet, and 41 is a resin-impregnated paper curing , 42 denotes plywood, alpha is the fine particles respectively.

  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 impregnated paper layer 41 is laminated on a plywood 42. A decorative sheet 2 having a surface protective layer 21 made of an ionizing radiation curable resin is stuck on a paper cured layer 41 via an adhesive layer 3. Further, the cured resin impregnated paper layer 41 prevents the surface irregularities of the plywood 42 from appearing on the surface layer when the flooring material 1 is used, and the drop impact resistance and caster resistance when the flooring material 1 is used. It is provided to improve the performance. As the plywood 42, for example, plywood made of lauan material, plywood using a single plate (small-diameter wood veneer) connected to the surface layer, a plywood made of afforestation material (pre-cured wood), or a conifer such as pine wood A plywood or a plywood using a single plate such as a small-diameter tree, a plantation material, or a conifer on the surface layer can be mentioned, and a plurality of single plates having different fiber directions, for example, three layers, five layers, seven layers. In which the fiber direction of the surface layer is configured in parallel with the longitudinal direction of the plywood, or the fiber direction of the surface layer is configured in a direction orthogonal to the longitudinal direction of the plywood, Is also good. 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.

The resin-impregnated paper cured layer 41 is integrated with the plywood 42 by placing a resin-impregnated paper impregnated with diallyl phthalate resin (hereinafter referred to as DAP resin) on the plywood 42 and hot pressing it. The composite material 4 can be obtained. The hot pressing conditions 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 600 seconds. Examples of the impregnated base material used for the resin-impregnated paper include paper base materials such as kraft paper, titanium paper, and cotton cloth, or cloth base materials such as woven cloth and non-woven cloth made of various materials. An amount of about 140 to 200 g / m ² is appropriate. If the basis weight is less than 140 g / m ² , surface defects may appear on the surface of the decorative sheet due to the influence of surface defects such as base material duck of plywood, base material surface, cracks, or surface irregularities. In addition, the caster resistance and the drop impact resistance cannot be improved, and if the basis weight is more than 200 g / m ² , the impregnated base material is impregnated with a longer time, resulting in poor productivity. At the same time, the cost increases, and the resin does not penetrate into the center of the impregnated base material and remains in the state of the impregnated base material. Therefore, the interlayer strength is weak, and there is a risk of delamination. Examples of the DAP resin impregnated in the impregnated base material include one or more diallyl phthalate monomers such as diallyl terephthalate monomer, diallyl orthophthalate monomer, diallyl terephthalate prepolymer, and diallyl orthophthalate prepolymer, or one or more of the above diallyl Examples thereof include a mixture of one or more phthalate monomers or prepolymers and an unsaturated polyester, and a mixture in which an acrylate is added. Although not shown, the resin-impregnated paper cured layer 41 is formed on both surfaces of the plywood 42 by placing the resin-impregnated paper impregnated with the DAP resin on both surfaces of the plywood 42 and performing hot pressure molding in the same manner as described above. It is also possible to provide a composite material provided with the above-described structure, and thus, warping and twisting during processing, or warping and twisting of a flooring material over time is prevented as compared with the composite material 4 described above. can do.

  Examples of the DAP resin include known peroxide-based curing agents such as benzoyl peroxide, t-butyl perbenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, cyclohexanone peroxide, and t-butyl peroxide. Alternatively, well-known azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutylnitronitrile, 2,2′-azobis-2-2,4-dimethylvaleronitrile, etc. A curing agent is added. Moreover, you may add a hardening accelerator, a hardening inhibitor, an internal mold release agent, a photoinitiator, a filler, etc. as needed.

As a method of impregnating the impregnated base material with the DAP resin, the DAP resin in solution may be impregnated by well-known double-sided or single-sided coating such as dipping method, roll coating method, gravure coating method, and dried. It is. The coating amount of the DAP resin after drying is generally 50 to 300 g / m ² , preferably 70 to 250 g / m ² .

  Next, the adhesive layer 3 for adhering the decorative sheet 2 having the surface protective layer 21 made of an ionizing radiation curable resin, which will be described later, and the resin-impregnated paper cured layer 41 of the composite material 4 will be described. 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, and 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 adhesive described above, generally 10 to 50 g / m ² as solids, preferably 25~40g / m ^2. The application surface of the adhesive may be the surface opposite to the surface protective layer 21 of the decorative sheet 2 described later, or may be the resin impregnated paper cured layer 41 surface.

  Next, the decorative sheet 2 having the surface protective layer 21 made of an ionizing radiation curable resin will be described. FIG. 2 is a layer configuration diagram schematically showing the first embodiment of the decorative sheet constituting the flooring of the present invention, and the decorative sheet 2 is one side of the synthetic resin transparent sheet 22 as a synthetic resin sheet base material. After embossing the surface, a concavo-convex pattern 6 is provided, and a wiping process is performed thereon to fill the concave portion of the concavo-convex pattern 6 with wiping ink 7, and then a primer layer 5 is provided on the entire exposed surface. A surface protective layer 21 made of an ionizing radiation curable resin is formed on the layer 5, and a pattern printing layer 8 and a solid pattern printing layer 8 ′ are formed on the other surface of the synthetic resin transparent sheet 22 via a primer layer 5 ′. These are printed in order. In the decorative sheet 2, the solid pattern printed layer 82 of the decorative sheet 2 and the resin-impregnated paper 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 the decorative sheet constituting the flooring material of the present invention. The decorative sheet 2 is at least a synthetic resin sheet 22 ′ as a synthetic resin sheet base material. A primer layer 5 ″ is provided on one surface, and a solid pattern printing layer 8 ′ and a pattern printing layer 8 are sequentially printed on the primer layer 5 ″, and the adhesive layer is further formed on the entire surface on the pattern printing layer 8 side. The synthetic resin transparent sheet 22 is bonded by a well-known dry lamination method through an adhesive layer 3 ′ formed of a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component as described in 3. The surface of the resin transparent sheet 22 is embossed to provide a concavo-convex pattern 6, and then, similarly to the case shown in FIG. The ink 7 was charged, further a primer layer 5 provided on the surface is obtained by forming a surface protective layer 21 made of an ionizing radiation curable resin on the primer layer 5. In the decorative sheet 2, the synthetic resin sheet 22 ′ of the decorative sheet 2 and the resin-impregnated paper 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 decorative sheet | seat shown in FIG.2, 3 showed the embodiment which carried out the embossing and the wiping process, these should just be provided as needed and are not essential.

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

  Next, various materials constituting the decorative sheet 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. 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, 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 radically polymerizable unsaturated group, photoinitiators are 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, 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 were included only in the surface protective layer 21 of the decorative sheet 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 sheet 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 adipic acid 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) may be any isocyanate that 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 decorative sheet 2 of FIG. 2 and 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 sheet constituting the flooring of the present invention, and the decorative sheet 2 ′ is the decorative sheet 2 of the second embodiment shown in FIG. A backer material 9 is laminated on the surface of the synthetic resin sheet 22 ′ through an adhesive layer 3 ″ made of the same resin as the adhesive layer 3 described above. In this case, although not shown, the decorative sheet 2 ′ is used in place of the decorative sheet 2 shown in FIG. The material 9 and the resin-impregnated paper cured layer 41 of the composite material 4 are bonded together via the adhesive layer 3 to form the flooring 1. The backer material 9 is in consideration 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, but a polyester-based sheet is preferable, and the backer material 9 has a corona discharge treatment on a necessary surface, if necessary. Easy adhesion treatment such as ozone treatment, plasma treatment, etc. In addition, although not shown, the backer material 9 is the back side of the decorative sheet 2 of the first embodiment shown in FIG. 5 can be applied to the floor sheet 1. The decorative sheet as shown in Fig. 5 using the backer material in the layer structure makes the flooring material 1 drop impact resistant, although the cost increases. And caster resistance can be further improved.

  In the above description, the decorative sheet 2 or 2 ′ provided with the surface protective layer 21 on the surface layer has been described. However, 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 is formed after the decorative sheet 2, 2 ′ before forming the primer layer 5 and / or the surface protective layer 21 is laminated on the composite material 4. Alternatively, the surface protective layer 21 may be provided after the decorative sheet 2 before forming the surface protective layer 21 in FIG. 4 is laminated on the composite material 4. . Although not shown, instead of the decorative sheets 2 and 2 ′ shown in FIGS. 2 to 5, the thickness of 0.15 to 0.7 mm, preferably 0.15 to 0.3 mm, oak, oak, A veneer decorative sheet with paper or non-woven fabric bonded to the back of the veneer, such as beech, zelkova, oak, etc. in consideration of dryness prevention and workability may be used. It may be. In this case, as a matter of course, the surface protective layer 21 is provided after the veneer decorative sheet is laminated on the composite material 4. Although not shown, instead of the decorative sheets 2 and 2 ′ shown in FIGS. 2 to 5, a synthetic resin film, for example, the above-described polypropylene plate is bonded to one surface of a polypropylene film, and then the polypropylene film is used. A laminated decorative sheet made of a synthetic resin film and a veneer, which is embossed from the side and then provided with a surface protective layer made of an ionizing radiation curable resin on the polypropylene film surface, may be used.

Next, the present invention will be described in further detail with reference to examples.
[Production of decorative sheet]
A urethane / nitrified cotton primer layer (2 g / m ² as a solid content) is formed on one surface of a colored polypropylene film having a thickness of 60 μm subjected to double-sided corona discharge treatment by gravure printing, and two liquids are formed on the other surface. After forming a solid pattern printing layer with a curable urethane printing ink and a woodgrain pattern printing layer on the solid pattern printing layer by a gravure printing method, the entire surface of the pattern printing layer is bonded with a two-component curable urethane resin. A polypropylene thermoplastic elastomer with an adhesive layer (2 g / m ² as solid content) and a benzotriazole UV absorber and a hindered amine radical scavenger added to the adhesive layer surface is heated and melt extruded with a T-die extruder. Forming a transparent resin layer having a thickness of 80 μm, and then providing an uneven pattern with an embossed plate of wood grain conduit pattern on the transparent resin layer surface, and the transparent resin layer surface A transparent primer layer (2 g / m ² as a solid content) is formed on the entire surface by applying a two-component curable urethane resin containing an acrylic / urethane block copolymer as a main component and isocyanate as a curing agent. A urethane acrylate ionizing radiation curable resin is applied to the entire surface of the primer layer and an electron beam (acceleration voltage: 175 KeV, irradiation amount: 5 Mrad) is irradiated to form a transparent surface protective layer (20 g / m ² as solid content). A decorative sheet was prepared.

Resin impregnation in which DAP resin (120 g / m ² ) is impregnated on impregnated base material (60 g / m ² kraft-no-size paper) on one side of lauan plywood (5 ply) connected to a 12 mm thick surface veneer Place paper and place duralumin mirror plates on both sides and heat press mold (processing conditions: temperature 140 ° C., pressure 10 kg / cm ² , pressurization time 5 minutes), resin impregnated paper on one side of plywood A composite material 1 having a resin-impregnated paper cured layer formed of The moisture-curable hot-melt adhesive to the resin-impregnated paper hardened layer surface of the composite material 1 [Nippon NSC Ltd.: 159TU (trade name)] was prepared above as well as 40 g / m ² coated by a roll coating method The decorative sheet was laminated so that the surface protective layer was exposed to obtain a flooring.

A flooring was obtained in the same manner as in Example 1 except that 120 g / m ² of Kraft-no-size paper was used as the impregnated base material.

A flooring was obtained in the same manner as in Example 1 except that 140 g / m ² of kraft-no-size paper was used as the impregnation base material.

A flooring was obtained in the same manner as in Example 1 except that 200 g / m ² of kraft-no-size paper was used as the impregnation base material.

A flooring was obtained in the same manner as in Example 1 except that 220 g / m ² of Kraft-no-size paper was used as the impregnated base material.

  The flooring materials of Examples 1 to 5 produced above were evaluated for caster resistance, drop impact resistance, and surface smoothness by the following evaluation methods. The results are summarized in Table 1.

  Evaluation of caster resistance: A load of 70 kg was applied to a jig provided with three polyamide wheels (diameter: 75 mm, width: 25 mm) with a diameter of 260 mm and an interval of 120 degrees, and the jig was moved at a speed of 20 rpm every 5 minutes. The test was carried out by reversing the rotation direction and rotating 1000 times, and the dent depth (unit: μm) of the flooring at that time was measured. The smaller the dent depth, the better the caster resistance. In addition, as an evaluation standard, a depth of 70 μm or less is indicated as “good” by ○, and a mark exceeding 70 μm is indicated by “x” as defective.

  Drop impact resistance evaluation: 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 dent depth (unit: μm) of the flooring at that time is measured. It was measured. The smaller the dent depth, the better the impact resistance. In addition, as evaluation criteria, the depth of less than 380 μm was indicated by a good mark, and 380 μm or more was indicated by a poor mark.

  Surface smoothness: Evaluated by visual inspection, single-plate joints on the surface of the plywood substrate do not appear on the decorative sheet surface, and those that are not noticeable are marked as good, and those that are noticeable are marked as bad and marked as bad evaluated.

  As is apparent from Table 1, the flooring materials of Examples 3 and 4 were able to have excellent performance in any of caster resistance, drop impact resistance, and surface smoothness.

It is a figure showing the basic layer composition of the flooring concerning the present invention diagrammatically. It is a layer lineblock diagram showing diagrammatically a 1st embodiment of a decorative sheet which constitutes a flooring of the present invention. It is a layer block diagram which shows schematically 2nd Embodiment of the decorative sheet which comprises the flooring of this invention. It is a layer block diagram which shows diagrammatically 3rd Embodiment of the decorative sheet which comprises the flooring of this invention. It is a layer block diagram which shows diagrammatically 4th Embodiment of the decorative sheet which comprises the flooring of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flooring material 2,2 'Decorative sheet 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 pattern 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 (9)

The resin-impregnated paper impregnated with diallyl phthalate resin is placed on one surface of the plywood, the resin-impregnated paper is cured by hot pressing to cure the resin-impregnated paper, and the resin-impregnated paper cured layer is integrated with the plywood. In a flooring in which a decorative sheet having a surface protective layer made of an ionizing radiation curable resin is laminated on the surface of the impregnated paper cured layer through an adhesive layer, the impregnated base material used for the resin impregnated paper is 140 g / m ² or more Floor material characterized by being 200 g / m ² or less. The flooring according to claim 1, wherein the decorative sheet is made of a synthetic resin sheet base material. The floor material according to claim 2, wherein the synthetic resin sheet base material is made of an olefin-based thermoplastic resin. The surface protective layer is formed on the synthetic resin sheet base material via a primer layer formed from a copolymer of acrylic resin and urethane resin and isocyanate. Crab flooring. The flooring material according to claim 2, wherein a backer material is laminated on a surface of the synthetic resin sheet base material on the adhesive layer side. The flooring according to claim 1, wherein the decorative sheet is made of a paper-based sheet base material. The flooring according to any one of claims 1 to 6, wherein the surface protective layer is a layer containing fine particles. The flooring according to claim 1, wherein at least a surface layer of the plywood is any one of a veneer made of a small diameter tree, a veneer made of a plantation material, and a veneer made of a conifer. A resin-impregnated paper impregnated with diallyl phthalate resin is placed on the other surface of the plywood, and the resin-impregnated paper cured layer integrated with the plywood is formed by hot pressing to cure the resin-impregnated paper. The flooring material according to any one of claims 1 to 8, wherein:

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