JP2006056075A - Decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material hard to receive the effect of water, having surface physical properties such as scratch resistance or anti-staining properties, especially excellent in falling impact resistance, used for especially providing a floor material or a top panel of a desk or a cabinet at a moderate cost and having appearance excellent in smoothness reduced in unevenness. <P>SOLUTION: In the decorative material having a decorative sheet wherein a surface protective layer comprising an ionizing radiation curable resin is provided on one side of plywood, an impact dispersing layer containing inorganic fine particles is provided between the plywood and the decorative sheet. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative material having resistance to a drop impact, and more particularly to a decorative material usable for a flooring material having resistance to a drop impact or a top plate of a desk or cabinet. .

  Conventionally, a decorative material such as a flooring material in which a decorative sheet is attached to a wooden base material is known. As the decorative sheet used for the decorative material, a surface protective layer made of a curable resin is usually provided on the surface in order to ensure the required surface properties, that is, scratch resistance and contamination resistance. . In addition, as the wooden base material used for it, a plywood using a lauan material is usually used, but a decorative material made of such a plywood is a caster part of furniture with casters, a chair or a desk, etc. When a load is applied to the tip of the leg, 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. (For example, refer to Patent Document 1).

Therefore, a decorative material using a composite material in which a medium-density fiberboard, so-called MDF is laminated, is employed on the surface of the plywood on the side where the decorative sheet is attached as a wooden base material. Although it was possible to solve the problem of the decorative material using the wood base material, the decorative material made of composite material using such a medium density fiberboard cost much more than the decorative material made of plywood alone. In addition, the medium density fiberboard absorbs water and swells, and the floor surface is likely to be wavy. Therefore, there is a problem that it is particularly difficult to use on floors such as kitchens where water is easily scattered.
JP 2001-193267 A

  Therefore, the present invention has been made in view of the above problems, and the first object is to be hardly affected by water, have surface physical properties such as scratch resistance and contamination resistance, and in particular drop resistance. It is to provide cosmetic materials that are excellent in impact properties, especially flooring materials, or top plates such as desks and cabinets at a reasonable cost. The second purpose is to provide a smooth appearance with few irregularities. It is to provide a decorative material, particularly a flooring material, or a top plate such as a desk or cabinet at a reasonable cost.

  In order to achieve the above object, the present inventor provides a cosmetic material having a decorative sheet provided with a surface protective layer made of an ionizing radiation curable resin on one surface side of a plywood. And an impact dispersion layer containing inorganic fine particles between the plywood and the decorative sheet.

  According to a second aspect of the present invention, in the decorative material according to the first aspect, the impact dispersion layer is characterized in that the inorganic fine particles have a laminated structure in the thickness direction.

  The present invention according to claim 3 is the decorative material according to any one of claims 1 and 2, wherein the inorganic fine particles have a Mohs hardness of 3.0 to 9.0. Is.

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

  The present invention according to claim 5 is the decorative material according to claim 4, characterized in that the synthetic resin sheet base material is made of an olefin-based thermoplastic resin.

  Moreover, the present invention according to claim 6 is the decorative material according to any one of claims 4 and 5, 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.

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

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

  The decorative material of the present invention does not swell even when water penetrates, and has the effect of being particularly excellent in drop impact resistance and surface smoothness.

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram schematically showing a layer configuration of a first embodiment of a decorative material according to the present invention, and FIG. 2 is a diagrammatic illustration of the function of an impact dispersion layer when a drop impact is applied to the decorative material shown in FIG. FIG. 3 is a diagram schematically showing the layer structure of a second embodiment of the decorative material according to the present invention, and FIG. 4 shows the first embodiment of the decorative sheet constituting the decorative material of the present invention. FIG. 5 is a schematic diagram of the layer configuration, FIG. 5 is a schematic diagram of the second configuration of the decorative sheet constituting the decorative material of the present invention, and FIG. 6 is a schematic diagram of the decorative sheet constituting the decorative material of the present invention. FIG. 3 is a diagram showing a layer configuration schematically showing three embodiments, in which 1, 1 ′ is a decorative material, 2 is a decorative sheet, 3, 9 is an adhesive layer, 4 is an adhesive layer in which inorganic fine particles are dispersed, 5, 5 ', 5 "are primer layers, 6 are uneven patterns, 7 are wiping inks, 8 is a pattern printing layer, 8' is a solid printing layer, and 21 is a surface. Protective layer, the synthetic resin transparent sheet 22, 22 'denotes a synthetic resin sheet, 23 is a paper based sheet, 41 is an impact dispersing layer, 42 is plywood, alpha inorganic fine particles, beta is a fine, respectively.

  FIG. 1 is a diagram schematically showing a layer structure of a first embodiment of a decorative material according to the present invention. The decorative material 1 has an impact dispersion layer 41, an adhesive layer 3, and ionizing radiation on one surface of a plywood 42. A decorative sheet 2 having a surface protective layer 21 made of a curable resin is laminated in order. 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 decorative material 1 is formed by fitting the female fruit and the male fruit between the decorative materials 1. Laying on the floor.

  Further, the impact dispersion layer 41 may be a thermoplastic resin or a curable resin as long as it is a resin that adheres to the plywood, and is not particularly limited. Curing resins that are less susceptible to changes, such as acrylic resins, phenolic resins, urea resins, unsaturated polyester resins, polyurethane resins, epoxy resins, melamine resins, diallyl phthalate resins, etc. Is formed by applying a solution in an appropriate solvent and dispersing inorganic fine particles α on the one surface of the plywood 42 by a known coating method such as a roll coating method. (In the case of a curable resin, it can be formed by further curing). The impact dispersion layer 41 may be colored with a pigment or the like as necessary.

As the inorganic fine particles α, those having a Mohs hardness in the range of 3.0 to 9.0 are preferable, and the material can be used without any particular limitation. For example, calcium carbonate, aluminum hydroxide, Examples thereof include silica and glass beads, and these may be used alone or in combination. When the Mohs hardness is less than 3.0, it is too soft, and when the Mohs hardness is more than 9.0, the shock is highly likely to propagate straight to the plywood 42. It becomes difficult to perform the function of the dispersion layer 41. In addition, as the particle size and dispersion amount of the inorganic fine particles α, it is preferable that the inorganic fine particles α have a laminated structure in the thickness direction in the impact dispersion layer 41, and it is necessary to consider the particle size and the dispersion amount. There is. The impact dispersion layer 41 is preferably applied so as to be 40 g / m ² after drying, because it is necessary to absorb the unevenness of the plywood and make the surface smoother than the uneven surface of the plywood. In consideration of cost, it is preferable that the coating amount after drying is 60 g / m ² or less. The particle size is generally selected from the range of 0.5 to 10 μm, and the dispersion amount is suitably dispersed in the range of 100 to 350 parts by weight with respect to 100 parts by weight of the resin. In addition, the particle size of the inorganic fine particles α to be dispersed is a mixture of a large particle size and a small particle size within the above range in an appropriate blending than those in which the single particle size is dispersed within the above range. It is possible to improve the impact resistance when the impact dispersion layer 41 is formed using a dispersion of the above. This is considered to be because the inorganic fine particles α having a small particle diameter are arranged between the large particle diameters, and a close-packed structure like a so-called stone wall is adopted. The particle size means the average particle size.

Next, the adhesive layer 3 for adhering the decorative sheet 2 having the surface protective layer 21 made of an ionizing radiation curable resin to be described later and the impact dispersion layer 41 will be described. The adhesive layer 3 may be formed by a known dry lamination method or wet lamination 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. The modified body which can be mentioned can be mentioned. 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. Using moisture-curable hot-melt adhesive such as emissions prepolymer those may. As the coating amount of the adhesive layer 3, approximately 10 to 50 g / m ² as solids, preferably 25~40g / m ^2, the coated surface of the adhesive, the surface protective layer of the decorative sheet 2 to be described later 21 may be the opposite surface or the impact dispersion layer 41 surface.

As shown in FIG. 2, the decorative material 1 configured as described above has a laminated structure in which a drop impact force F is dispersed in the impact dispersion layer 41 as shown in FIG. 2 when a drop impact is applied from the decorative sheet 2 side described later. Since the impact force F is propagated to the plywood 42 as F ₁ (in FIG. 2, the impact force F ₁ is divided into four directions) by the inorganic fine particles α, the impact force on the plywood 42 Can be relaxed, and the drop impact resistance can be improved, and the dents in the plywood and thus the dents in the decorative material can be reduced.

FIG. 3 is a view schematically showing the layer structure of the second embodiment of the decorative material according to the present invention. The decorative material 1 ′ is an adhesive layer 4 in which inorganic fine particles α are dispersed on one surface of a plywood 42. And a decorative sheet 2 having a surface protective layer 21 made of an ionizing radiation curable resin. The adhesive layer 4 can be formed using the same adhesive as described in the adhesive layer 3 in the first embodiment described above, and the inorganic fine particles α dispersed in the adhesive layer 4 are also described above. The same kind and the same particle size as described in the above can be used, and the amount of dispersion is the same as above. The coating amount may be adjusted so that the adhesive strength and the inorganic fine particles α take a laminated structure in the thickness direction of the adhesive layer 4, but generally 40 to 100 g / m ² after drying. It may be applied so that 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 the plywood 42 surface. The decorative material 1 ′ thus configured can improve the drop impact resistance because the adhesive layer 4 functions in the same manner as the impact dispersion layer 41 described in the first embodiment, and the plywood dent. As a result, the dent of the cosmetic material can be reduced. The adhesive layer 4 may be colored with a pigment or the like as necessary.

  Next, the decorative sheet 2 having the surface protective layer 21 made of an ionizing radiation curable resin will be described. FIG. 4 is a layer configuration diagram schematically showing a first embodiment of the decorative sheet constituting the decorative material of the present invention. The decorative sheet 2 is one of the synthetic resin transparent sheets 22 as a synthetic resin sheet base material. After embossing the surface, a concavo-convex pattern 6 is provided, and after wiping treatment is performed to fill the concave portion of the concavo-convex pattern 6 with wiping ink 7, a primer layer 5 is provided on the entire exposed surface, and the primer 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 and formed in order. The decorative sheet 2 is formed by bonding the solid pattern printed layer 8 ′ of the decorative sheet 2 and the impact dispersion layer 41 as the first embodiment via the adhesive layer 3, or the decorative sheet 2 2 of the solid pattern printing layer 8 ′ and the plywood 42 as the second embodiment are bonded through the adhesive layer 4.

  FIG. 5 is a layer configuration diagram schematically showing a second embodiment of the decorative sheet constituting the decorative 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. A synthetic resin transparent sheet 22 is bonded by a well-known dry lamination method through an adhesive layer 9 formed of a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component, as described in 3, and the synthetic resin. The surface of the transparent sheet 22 is embossed to provide a concavo-convex pattern 6, and thereafter, similarly to the case shown in FIG. The ink 7 was charged, further a primer layer 5 provided on the surface, and forming a surface protective layer 21 made of an ionizing radiation curable resin on the primer layer 5. The decorative sheet 2 is formed by bonding the synthetic resin sheet 22 ′ of the decorative sheet 2 and the impact dispersion layer 41 as the first embodiment via the adhesive layer 3, or the decorative sheet 2 2 of the synthetic resin sheet 22 ′ and the plywood 42 as the second embodiment are bonded via the adhesive layer 4. The synthetic resin sheet 22 'is generally a colored sheet, but may be a non-colored sheet. The decorative sheet shown in FIGS. 4 and 5 shows an embodiment in which embossing and wiping are performed. However, the decorative sheet used in the present invention is not limited to this, and a mirror-finished cosmetic having excellent surface smoothness. It may be a sheet.

  FIG. 6 is a layer configuration diagram schematically showing a third embodiment of the decorative sheet constituting the decorative material 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. Solid print layer 8 ′ and pattern print layer 8 are printed in order, and surface protective layer 21 made of ionizing radiation curable resin containing fine particles β described later is formed on the entire surface on the pattern print layer 8 side. It is. The decorative sheet 2 is formed by bonding the paper-based sheet 23 of the decorative sheet 2 and the impact dispersion layer 41 as the first embodiment via the adhesive layer 3, or the decorative sheet 2 The paper sheet 23 and the plywood 42 as the second embodiment are bonded via the adhesive layer 4.

  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.

  The paper-based sheet 23 includes thin paper, craft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, Latex-impregnated paper can be mentioned, woven fabric or non-woven fabric using inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, carbon fiber, etc., organic resin such as polyester, vinylon, etc. Can be mentioned.

  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. 4 to 6 show the configuration in which both the pattern printing layer 8 and the solid pattern printing 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 β (see FIG. 6). The fine particles β (see FIG. 6) may have protrusions and corners on the surface of the fine particles, but a spherical shape, an 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 causing wear. The average particle diameter of the fine particles β needs to be selected and used depending on the coating thickness of the surface protective layer 21, but basically the fine particles β are partially exposed from the surface protective layer 21. Usually, the average particle size is about 5 to 100 μm. The ratio of the fine particles β 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 β were included only in the surface protective layer 21 of the decorative sheet 2 of the third embodiment shown in FIG. 6, 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 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 decorative sheet 2 of FIG. 4 and FIG. 5, the thing of the structure which provided the primer layer (The layer shown by the code | symbol 5, 5 ', 5''on FIG. 4, 5) was shown, It is a specification that meets the high level requirements as a cosmetic material, and when the required level as a cosmetic material is low, these primer layers (layers indicated by reference numerals 5, 5 ′, 5 ″ in FIGS. Further, in FIG. 6, 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.

  In addition, until now, it has been described that the decorative sheet having the surface protective layer 21 provided on the surface layer is bonded. However, the decorative material of the present invention is not limited to this, for example, the above-described cosmetic materials in FIGS. The decorative sheet 2 before forming the primer layer 5 and / or the surface protective layer 21 is adhered to the surface of the impact dispersion layer 41 as the first embodiment or the surface of the plywood 42 as the second embodiment. The primer layer 5 and / or the surface protective layer 21 may be provided later, and the decorative sheet 2 before forming the surface protective layer 21 in FIG. 6 is used as the first embodiment. The surface protective layer 21 may be provided after being attached to the surface of the impact dispersion layer 41 or the surface of the plywood 42 as the second embodiment. In addition, the decorative material of the present invention may have a configuration in which the impact dispersion layer 41 is provided on the other surface of the plywood 42 (the surface opposite to the surface on which the decorative sheet 2 is provided). And warping and twisting of the cosmetic material over time can be prevented. Further, although not shown, the decorative material of the present invention may be the adhesive layer 4 shown in FIG. 3 instead of the adhesive layer 3 in the decorative material of the first embodiment shown in FIG. . By comprising in this way, it can be further excellent in the tolerance with respect to a drop impact.

Next, the present invention will be described in more detail with reference to the following examples.
First, on one side of a 12 mm thick lauan plywood (5 ply), a two-component curable paint with an isocyanate curing agent added [100 parts by weight of an acrylic resin solution (solid content 30%) with calcium carbonate (average particle size) (Diameter: 0.63 μm) 100 parts by weight of paint) was applied by a roll coating method to 50 g / m ² after drying, and then placed in a drying oven at 60 ° C. for 20 minutes for impact dispersion on one surface. A plywood having a layer formed thereon (hereinafter referred to as an impact dispersion plywood) was produced.

[Production of decorative sheet of 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 as irradiation to prepare a decorative sheet of the first embodiment to form a surface protective layer of 20 g / m ² a.

[Production of decorative sheet of third embodiment]
Solid pattern printing by gravure printing method using printing ink made of acrylic-urethane resin (resin with 5 parts by weight of hexamethylene diisocyanate added to 100 parts by weight of acrylic polyol) on one side of 50 g / m ² acrylic latex impregnated paper A layer and a woodgrain pattern print layer were formed. Thereafter, an ionizing radiation curable resin [Daiichi Seika Kogyo Co., Ltd.] with 15 parts by weight of α-alumina (manufactured by Showa Denko KK: AS-30 (trade name)) as spherical fine particles on the entire printed surface is added. EBF-04 (trade name)] is applied and dried by a roll coating method and then irradiated with an electron beam (175 KeV, 5 Mrad) to form a surface protective layer having a solid content of 30 g / m ^2. A sheet was produced.

[Experiment 1]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Ricabond BA-10L (100 parts by weight) with BA-11B (2.5 parts by weight) added to the surface of the impact dispersion layer of the impact dispersion plywood produced above Agent] is applied using a roll coating method so as to be about 41 g / m ² after being dried, and the decorative sheet according to the first embodiment prepared above is applied to the application surface with the solid print layer on the adhesive surface. Thus, a decorative material was obtained.

[Experiment 2]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Ricabond BA-10L (100 parts by weight) with BA-11B (2.5 parts by weight) added to the surface of the impact dispersion layer of the impact dispersion plywood produced above Agent] is applied using a roll coating method so as to be about 41 g / m ² after drying, and the decorative sheet of the third embodiment prepared above is applied to the application surface so that the paper surface is located on the adhesive surface. Combined to obtain a cosmetic material.

[Experiment 3]
An adhesive in which inorganic fine particles are dispersed is applied to one side of a 12 mm thick lauan plywood (5 ply) separately prepared by using a roll coating method so that it is about 85 g / m ² after drying. The decorative sheet of the first embodiment prepared above was bonded so that the solid print layer was positioned on the adhesive surface to obtain a decorative material.

[Experimental Example 4]
An adhesive in which inorganic fine particles are dispersed is applied to one side of a 12 mm thick lauan plywood (5 ply) separately prepared by using a roll coating method so that it is about 85 g / m ² after drying. The decorative sheet of the third embodiment produced above was bonded so that the paper surface was positioned on the adhesive surface to obtain a cosmetic material. The adhesive in which the inorganic fine particles described in Examples 3 and 4 are dispersed is manufactured by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-10L (100 parts by weight) with BA-11B (2.5 parts by weight). This is an adhesive in which 100 parts by weight of a mixture of aluminum hydroxide having an average particle diameter of 1 μm and 10 μm mixed at a weight ratio of 1: 1 is dispersed.

[Experimental Example 5]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-10L (100 parts by weight) BA-11B (2.5 parts by weight) on one side of a 12 mm thick lauan plywood (5 ply) prepared separately Is applied using a roll coat method so as to be about 41 g / m ² after drying, and the decorative sheet of the first embodiment prepared above is applied so that the surface protective layer is exposed. Combined to obtain a cosmetic material.

[Experimental example 6]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-10L (100 parts by weight) BA-11B (2.5 parts by weight) on one side of a 12 mm thick lauan plywood (5 ply) prepared separately Is applied using a roll coat method so as to be about 41 g / m ² after drying, and the decorative sheet of the third embodiment prepared above is applied so that the surface protective layer is exposed. Combined to obtain a cosmetic material.

  About the decorative material of Experimental Examples 1-6 produced 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 dent of the decorative material at that time (Unit: μm) was measured. The smaller the dent depth, the better the impact resistance. In addition, the numerical value of Table 1 is an average value which carried out the impact test 10 times about each decorative material.

  As is clear from Table 1, the decorative materials of Experimental Examples 1 to 4 showed excellent performance with small dents in terms of drop impact resistance as compared with the decorative materials of Experimental Examples 5 and 6.

It is a figure showing the layer composition of a 1st embodiment of the cosmetics concerning the present invention diagrammatically. It is a principal part enlarged view which illustrates schematically the function of the impact dispersion layer when a drop impact is applied to the decorative material shown in FIG. It is a figure which shows diagrammatically the layer structure of 2nd Embodiment of the cosmetics concerning this invention. It is a layer block diagram which shows the 1st embodiment of the decorative sheet which comprises the decorative material of this invention schematically. It is a layer block diagram which shows the 2nd embodiment of the decorative sheet which comprises the decorative material of this invention schematically. It is a layer block diagram which shows the 3rd embodiment of the decorative sheet which comprises the decorative material of this invention schematically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,1 'Cosmetic material 2 Cosmetic sheet 3,9 Adhesive layer 4 Adhesive layer 5,5', 5 "Primer layer 6 Uneven pattern 7 Wiping ink 8 Picture printing layer 8 'Solid pattern printing layer 21 Surface Protective Layer 22 Synthetic Resin Transparent Sheet 22 ′ Synthetic Resin Sheet 23 Paper-Based Sheet 41 Impact Dispersion Layer 42 Plywood α Inorganic Fine Particle β Fine Particle

Claims (8)

In a decorative material having a decorative sheet provided with a surface protective layer made of an ionizing radiation curable resin on one surface side of a plywood, having a shock dispersion layer containing inorganic fine particles between the plywood and the decorative sheet Characteristic cosmetic material. The cosmetic material according to claim 1, wherein the impact dispersion layer has a laminated structure of the inorganic fine particles in the thickness direction. The cosmetic material according to claim 1, wherein the inorganic fine particles have a Mohs hardness of 3.0 to 9.0. The decorative material according to claim 1, wherein the decorative sheet is made of a synthetic resin sheet base material. The decorative material according to claim 4, wherein the synthetic resin sheet base material is made of an olefinic 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. Cosmetic material according to crab. The decorative material according to claim 1, wherein the decorative sheet is made of a paper-based sheet base material. The cosmetic material according to any one of claims 1 to 7, wherein the surface protective layer is a layer containing fine particles.

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