JP2012183834A - Decorative sheet, and decorative laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet preventing a wood surface or gloss of sliced veneer from being deteriorated, showing a sense of depth and a sense of irregularities as design, and excelling in contamination resistance and wear resistance, and to provide a decorative laminate using the same.SOLUTION: This decorative sheet is composed by laminating, on one surface of a sliced veneer, a propylene-based sheet layer composed by forming a pattern-like low-gloss print layer on one surface and thereafter forming a surface protecting layer throughout the one surface to expose the surface protecting layer. In the decorative sheet, the surface protecting layer is formed of a curable resin.

Description

  The present invention relates to a decorative sheet made of a veneer used for surface decoration of wall materials, artificial materials, building materials such as joinery and furniture, and a decorative plate formed by laminating the decorative sheet.

  Conventionally, for surface decorations such as wall materials, artificial materials, joinery materials such as joinery and furniture, plywood, particleboard, high density fiberboard (HDF), medium density as a cheaper material than solid wood A decorative board in which makeup such as a wood grain pattern is applied to the surface of a base material such as a fiber board (MDF) or the like, an inorganic board such as a calcium silicate board or a gypsum board is used. The veneer veneer with thin veneer slices of natural wood has a design similar to that of solid natural wood, so it is widely used as a cheap luxury veneer compared to natural wood. Yes.

  Generally, the veneer decorative board is composed of fiberboard such as plywood, particle board, high density fiber board (HDF), medium density fiber board (MDF), inorganic board such as calcium silicate board and gypsum board. The veneer is bonded to the surface of the material via an adhesive, and the veneer surface is painted as necessary. However, the veneer veneer is subject to dryness (along the grain) due to changes in temperature and humidity in the four seasons. There were problems such as frequent occurrence of fine cracks), and severe dry cracking, and the clothes were caught and damaged due to contact between the clothes and the veneer decorative plate. In recent years, it has been difficult to obtain the precious wood that is the raw material of the veneer, and the thickness of the veneer tends to be reduced to 0.1 to 0.3 mm, and the occurrence of dry cracks tends to increase accordingly. is there.

  As a method for improving this dry crack, proposals have been made to improve an adhesive for bonding a base material and a veneer (see, for example, Patent Documents 1 and 2). The technique disclosed in Patent Document 1 is intended to reduce dry cracking by combining an elastomer adhesive and non-sizing paper, and the technique disclosed in Patent Document 2 includes an aqueous polyvinyl alcohol solution and a carboxylated modified product. Necessary for viscosity adjustment by mixing the main component with synthetic rubber and latex as essential components, starch-based extender and curing agent with an isocyanate compound having two or more isocyanate groups in the molecule as essential components The base material and the veneer are bonded to each other by using an adhesive made of a composition to which an amount of water is added, thereby preventing dry cracks and the like.

  However, the veneer decorative plate is not limited to the above-mentioned problem. For example, in the case of a white-type veneer such as a flaw, it is difficult to remove the dirt when the dirt adheres to the surface of the veneer. However, since the color changes with the passage of time due to the influence of ultraviolet rays or the like, the original white color cannot be maintained, and the high-grade image is impaired.

Japanese Patent Publication No.58-56517 JP 59-202801 A

  Therefore, the present invention has been made in view of the above problems, and the purpose of the present invention is to have both a sense of depth and an unevenness visually as a design without impairing the bark and terry of the veneer, It is an object of the present invention to provide a decorative sheet excellent in stain resistance and abrasion resistance, and a decorative board using the decorative sheet.

  In order to achieve the above object, the present inventor provides a decorative sheet according to the first aspect of the present invention, wherein the one surface of the protruding plate is provided with a patterned low-gloss printing layer on one surface, and then the one surface is provided. A propylene-based sheet layer provided with a surface protective layer on the entire surface is laminated so that the surface protective layer is exposed.

  The present invention according to claim 2 is the decorative sheet according to claim 1, wherein the surface protective layer is made of a curable resin.

  Moreover, the present invention according to claim 3 is the decorative sheet according to claim 2, wherein the curable resin is an ionizing radiation curable resin.

  According to a fourth aspect of the present invention, in the decorative sheet according to any one of the first to third aspects, a backing paper is laminated on the other surface of the protruding plate.

  Further, the present invention according to claim 5 is the decorative sheet according to any one of claims 1 to 4, wherein among the layers constituting the decorative sheet, at least the propylene-based sheet layer constituting the exposed surface or the The surface protective layer contains at least an ultraviolet absorber.

  The decorative board of the present invention according to claim 6 is characterized in that the decorative sheet according to any one of claims 1 to 5 is pasted with a base material for decorative board through an adhesive layer. is there.

  The decorative sheet of the present invention and the decorative board using the same can utilize the bark and terry of the veneer as they are, and can express a natural texture peculiar to natural wood, and is provided with a patterned low-gloss printing layer. As a result, a design effect having a sense of depth and unevenness can be expressed visually, and at the same time, an effect excellent in contamination resistance and wear resistance is exhibited.

It is a layer block diagram which shows one Example of the decorative sheet concerning this invention schematically.

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a diagram showing the layer structure of an embodiment of a decorative sheet according to the present invention. In the figure, 1 is a decorative sheet, 2 is a propylene-based sheet layer, 3 is a primer layer, and 4 is a patterned low gloss. The printed layer, 5 is a surface protective layer, 6 is an adhesive layer, and 7 is a veneer.

  FIG. 1 is a diagram showing the layer structure of an embodiment of a decorative sheet according to the present invention. The decorative sheet 1 is provided with a primer layer 3 on one entire surface, and a patterned low gloss on the primer layer 3 surface. After the printing layer 4 is provided, the surface protective layer 5 is provided with a surface, a polyol component, and an isocyanate component so that the surface protective layer 5 exposes the propylene-based sheet layer 2 provided with the surface protective layer on the entire surface of the one surface. It is laminated through an adhesive layer 7 formed of a two-component curable urethane adhesive. By comprising in this way, the protrusion board 8 and the pattern-like low gloss printing layer 4 will be provided via the propylene-type sheet | seat layer 2, and the design effect with a feeling of depth (depth) can be expressed. Moreover, the pattern-like low gloss printing layer 4 part is visually recognized as a recessed part, and the design effect with an unevenness | corrugation feeling can be expressed. In the present invention, the patterned low gloss printing layer 4 is suitably a conduit pattern printing layer.

  Next, various materials constituting the decorative sheet 1 will be described. First, the propylene-based sheet layer 2 will be described. Examples of the propylene-based sheet layer 2 include a homopolypropylene composed of homopolymer of propylene, or a propylene-based sheet composed of a binary or ternary random copolymer or block copolymer copolymerized with ethylene, butene or the like. The propylene-based sheet layer 2 may be any layer as long as it does not damage the bark or terry of the veneer plate 8, and a transparent or translucent uncolored sheet is suitable. The thickness of the propylene-based sheet is generally 60 to 120 μm, and may be in an unstretched state or a stretched state in a uniaxial or biaxial direction. If the thickness is less than 60 μm, there is a risk that hot water may be generated due to drying during formation of the primer layer 3 or the surface protective layer 5 or heat during electron beam irradiation, and if it exceeds 120 μm, a significant cost-effective effect is expected. Can not. Further, the propylene-based sheet may be subjected to a known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on a necessary surface as necessary. In addition, the propylene-based sheet may be obtained by appropriately adding a known additive such as an antioxidant, a light stabilizer, and an ultraviolet light inhibitor.

  Next, the patterned low gloss print layer 4 will be described. The patterned low-gloss printing layer 4 is a region (low-gloss region) where the region provided with this layer is less glossy than the other regions. Although this mechanism has not yet been fully elucidated, when the uncured material of the surface-protective layer 5 made of the curable resin provided on the surface and the patterned low-gloss printed layer 4 is applied, It is presumed that the resin component of the patterned low-gloss printing layer 4 and the uncured product of the surface protective layer 5 exhibit some interactions such as elution, dispersion, and mixing depending on the combination of materials and application conditions. Is done. That is, the respective resin components in the uncured product of the curable resin that forms the patterned low-gloss printing layer 4 and the surface protective layer 5 are suspended without being completely compatible in a short time. It is considered that the portion present on or near the patterned low-gloss print layer 4 and in the suspended state scatters light to form a low-gloss region. Since the surface protective layer 5 is formed by crosslinking and curing while maintaining this suspended state, the region on the patterned low-gloss printing layer 4 in the surface protective layer 5 is at least a low-gloss region. By the illusion of, it is assumed that the area is recognized as if it were a recess. Further, depending on the type and application conditions of the ink for forming the patterned low gloss printing layer 4 and the curable resin composition for forming the surface protective layer 5, the outermost surface of the surface protective layer 5 may be In some cases, the glossy printed layer 4 is raised to form a convex shape. Since the surface of the surface protective layer 5 has such a convex shape, light is also scattered at this portion, which is preferable because the visual unevenness is further emphasized. In addition, about the height of the said convex shape, it is preferable that it is the height which is the range which has the effect of this invention, and is usually the range of 2-3 micrometers.

  The ink that forms the patterned low-gloss printing layer 4 has a property of causing interaction with the curable resin composition (uncured curable resin) that forms the surface protective layer 5, and is curable. It is appropriately selected in relation to the resin composition (uncured curable resin). Specifically, the ink vehicle preferably contains 50% by weight or more of a urethane resin or a polyvinyl acetal resin. The urethane-based resin is a polyol component such as an acrylic polyol, a polyester polyol, or a polyether polyol, and an isocyanate component such as an aromatic isocyanate such as tolylene diisocyanate, xylene diisocyanate, or diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Examples include urethane resins obtained by reacting with aliphatic or cycloaliphatic isocyanates such as hydrogenated tolylene diisocyanate (linearly cross-linked or network cross-linked). be able to. Moreover, a polyvinyl acetal type resin is obtained by condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of the polyvinyl acetal resin include polyvinyl formal (formal resin), polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral (butyral resin), and polyvinyl hexyl.

  If necessary, unsaturated polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer may be used to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and its surroundings. A gloss adjusting resin such as the above may be used in combination. The mixing ratio of the gloss adjusting resin is in the range of 10 to 90% by weight with respect to the total amount of the vehicle. If it is within this range, a sufficient enhancement effect of low gloss area expression can be obtained. The ink for forming the patterned low gloss printing layer 4 may be uncolored or may be colored by adding a colorant such as a pigment. Moreover, a recessed part becomes clearer and it can be set as the decorative sheet which show | plays the design effect excellent in the uneven | corrugated feeling and depth visually.

  In the present invention, the surface protective layer 5 is provided on the patterned low-gloss printing layer 4, and the curable resin composition (the ink constituting the patterned low-gloss printing layer 4 and the surface protective layer 5 ( The region on the patterned low-gloss printing layer 4 becomes at least a low-gloss region by the interaction with the uncured product of the curable resin, and the region is recognized as if it is a concave portion by the optical illusion. Is. The film thickness of the patterned low gloss printing layer 4 is suitably 0.5 μm or more and 5.0 μm or less in consideration of printability and interaction with the curable resin composition (uncured curable resin). is there.

  Further, it is preferable to incorporate extender pigments as fine particles in the printing ink for forming the patterned low gloss printing layer 4. By blending the extender, light scattering can be promoted and the low gloss effect can be further enhanced. The extender pigment is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink, is preferable. Silica is preferred.

  The average particle diameter of the silica may be larger than the film thickness (μm) of the patterned low-gloss printing layer 4 and is generally about 1.0 μm or more. The thickness of the protective layer 5 should be determined in relation to the film thickness (μm), but the film thickness of the surface protective layer 5 takes into consideration various physical properties required for a decorative sheet (post-processing suitability and proper use) and cost. It is generally 10.0 μm or less, preferably 7.0 μm or less, and the optimum range of the average particle diameter is 2.0 μm or more and 4.0 μm or less. The amount of the extender pigment added to the ink for forming the patterned low gloss print layer 4 is suitably 5 to 15 parts by weight with respect to 100 parts by weight of the ink composition other than the extender pigment. If the amount is less than 5 parts by weight, sufficient thixotropy cannot be imparted to the printing ink composition forming the patterned low-gloss printing layer 4, and if it exceeds 15 parts by weight, the effect of imparting low gloss is reduced. Therefore, it is not preferable.

  Next, the surface protective layer 5 will be described. This surface protective layer 5 is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, stain resistance, water resistance, weather resistance and the like required for the decorative sheet 1 (see FIG. 1). The resin for forming the surface protective layer 5 is suitably formed by using a curable resin such as a thermosetting resin or an ionizing radiation curable resin, but more preferably has a high surface hardness and high productivity. It is an ionizing radiation curable resin because it is excellent.

As thermosetting resins, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-ureas Examples thereof include a cocondensation resin, a silicon resin, and a polysiloxane resin. If necessary, a curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator is added to the resin. For example, as a curing agent, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. The radical initiator is added to the unsaturated polyester resin. As a method of forming the surface protective layer with the thermosetting resin, for example, the above thermosetting resin is made into a solution, applied by a known coating method such as a roll coating method or a gravure coating method, dried and cured. Can be formed. The coating amount of the surface protective layer is suitably about 1 to ²⁰ g / m ^{2 in} terms of solid content, and in particular, the film thickness of the patterned low gloss printing layer is 0.5 μm or more and 5.0 μm or less, When the average particle size is 1.0 μm or more and 7.0 μm or less, ² to 10 g / m ² in terms of solid content is appropriate.

  Next, the ionizing radiation curable resin will be described. The ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. is there. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The electron beam used is 100 to 1000 keV, preferably 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  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 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 sulfonate ester, a freeloxyxonium 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. The application method and application amount of the ionizing radiation curable resin are the same as those of the thermosetting resin, and the description thereof is omitted.

  When the surface protective layer 5 is given further scratch resistance and wear resistance, for example, inorganic particles such as α-alumina, silica, kaolinite, iron oxide, diamond, silicon carbide, etc. Is mentioned. Examples of the particle shape include a spherical shape, an elliptical shape, a polyhedral shape, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Examples of organic substances include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 3 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles. Moreover, the mixture ratio of the fine particles with respect to the curable resin forming the surface protective layer 5 is 1 to 80 parts by weight with respect to 100 parts by weight of the curable resin.

  Next, the primer layer 3 will be described. The primer layer 3 is provided for the purpose of improving the adhesive strength between the propylene-based sheet layer 2 and the patterned low gloss printing layer 4 or the surface protective layer 5. Examples of the resin used for the primer layer 3 include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and the like. It can be mixed to form a coating composition or an ink composition, and can be formed using an appropriate application means such as a roll coating method or a gravure printing method.

  However, the primer layer 3 is particularly preferably formed of a resin comprising (i) a copolymer of an acrylic resin and a urethane resin and (ii) an isocyanate. That is, the copolymer of (i) an acrylic resin and a urethane resin comprises an acrylic polymer component having a hydroxyl group at the terminal (component A), a polyester polyol component having a hydroxyl group at both ends (component B), and a diisocyanate component (component). C) is 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. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the terminal. This acrylic-polyester urethane copolymer is formed by reacting the terminal hydroxyl group with the isocyanate of (ii) and curing it.

  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, a layer in contact with the primer layer, for example, the ionizing radiation curable resin of the surface protective layer 5 and the conjugated double bond of the acrylic polymer react with each other. 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 3, the urethane resin component formed by the reaction between the component B and the component C imparts flexibility to the primer layer 3 and contributes to adhesiveness with the propylene-based sheet layer 2. Further, the acrylic resin component made of an acrylic polymer contributes to weather resistance and blocking resistance in the primer layer 3. 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. Examples of the diisocyanate include tetramethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4′-cyclohexyl. A diisocyanate etc. can be mentioned. 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 3 may be formed by coating by a known coating method such as a coating method. 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, a monomer such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or a multimer such as a dimer or trimer thereof, or And polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols. In addition, although the thing of the structure which provided the primer layer 3 was shown in the decorative sheet 1, 1 'of FIG. 1, FIG. 2, this is a decorative sheet specification corresponding to a high level request | requirement, and a required level is low. In some cases, the primer layer 3 is not necessarily provided.

As the coating amount after drying of the primer layer 3, a from 1 to 20 g / m ^2, preferably from 1 to 5 g / m ^2. Moreover, this primer layer 3 is good also as a layer which added additives, such as fillers, such as a silica powder, a light stabilizer, and a coloring agent, as needed.

  Although not shown, a primer layer is provided on the back surface of the propylene-based sheet layer 2 shown in FIG. 1 (the surface opposite to the surface on which the surface protective layer 5 is provided), and the propylene-based sheet layer 2 and the projecting plate 7 May be configured to improve the adhesive strength when the decorative sheet 1 is laminated by laminating through the adhesive layer 6. The primer layer provided on the back surface of the propylene-based sheet layer 2 may be appropriately provided as necessary when the adhesive force is insufficient. For example, the primer layer described above may also be used. The resin described in the layer 3 may be appropriately selected and used.

  In addition, the protruding plate 7 is not particularly limited as long as it is a thin plate obtained by slicing natural wood, but in the present invention, pine, cedar, firewood, or light, white A veneer obtained from natural wood (raw wood) is suitable. The thickness of the protruding plate 7 is suitably 0.1 to 0.5 mm.

  Although not shown, for the purpose of preventing dry cracking, improving waterproofness, or improving processability on the back surface of the protruding plate 7 (opposite surface on which the propylene-based sheet layer 2 is provided) Paper, inter-paper reinforced paper, resin-impregnated paper, non-woven fabric, woven fabric, or a three-layer structure of these via polyethylene or polypropylene, for example, inter-paper reinforced paper / polyethylene or polypropylene / inter-paper reinforced paper, or It may be a thin paper / polyethylene or polypropylene / thin paper, or a veneer with a configuration in which backing paper such as interleaf reinforced paper / polyethylene or polypropylene / aluminum foil, thin paper / polyethylene or polypropylene / aluminum foil is laminated with an adhesive. In addition, polyester film, polyamide film, polyolefin film One surface of an unstretched or stretched film such as aluminum, a vapor deposited film on which an inorganic substance such as aluminum, silicon oxide, aluminum oxide, indium oxide, tin oxide, or zirconium oxide is deposited, or at least one of the vapor deposited films A veneer having a configuration in which a backing paper obtained by laminating paper, inter-paper reinforcing paper, resin-impregnated paper, nonwoven fabric, woven fabric or the like with an adhesive layer is laminated on the surface may be used.

  In the present invention, as the projecting plate 7, a projecting plate obtained from pine, cedar, birch, or a light-colored, white-based natural wood (raw wood) is used. In order to change the color, it is necessary to maintain the original white hue so as not to impair the high-quality image. The surface protective layer 5, the patterned low gloss printing layer 4, the primer layer 3, the propylene For example, a known organic ultraviolet absorber such as benzotriazole-based, benzophenone-based, triazine-based, or the like having an average particle size of 5 to 5 is disposed on the surface side of the projecting plate 7 such as the system sheet layer 2 and the adhesive layer 6. Inorganic ultraviolet absorbers such as about 120 nm titanium dioxide, cerium oxide, zinc oxide, etc., or known light stabilizers such as hindered amines, antistatic agents, level It is preferable to add a known additive such as an adhesive, but at least the propylene-based sheet layer 2 or the surface protective layer 5 constituting the exposed surface of the decorative sheet 1 has the above-described organic ultraviolet absorber or inorganic system. It is preferable to add a known additive such as an ultraviolet absorber.

  Moreover, although not shown in figure, as an adhesive used for the said adhesive layer for sticking the decorative sheet 1 and the base material for decorative plates through an adhesive layer to make a decorative plate, for example, a thermoplastic resin Any type of adhesive, such as a system, a thermosetting resin system, and a rubber (elastomer) system, may be used. These may be known ones or commercially available products. Thermoplastic resin adhesives include polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, nitrocellulose, acetic acid Cellulose, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and the like can be mentioned. Examples of thermosetting resin adhesives include urea resins, melamine resins, phenol resins, Resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyamideimide, polybenzimidazole, polybenzothiazole, and the like can be given. Rubber-based adhesives include natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, Examples include block copolymer rubber (SBS, SIS, SEBS, etc.).

  Moreover, as the base material (not shown) for a decorative board used for making a decorative board, a medium-density fiber board (MDF), a high-density fiber board (HDF), a woody base material such as particle board, plywood, Or an inorganic base material, such as a cement board, a calcium silicate board, a gypsum board, a metal plate etc. can be mentioned. As the thickness of the base material for decorative plate, a thickness of 0.5 mm or more is appropriate for a metal plate, and 1.0 mm or more is suitable for practical use in other cases.

  Although not shown in the figure, the state of the laminated sheet of the surface protective layer 5 / patterned low gloss printing layer 4 / primer layer 3 / propylene-based sheet layer 2 before laminating the protruding plate 7 via the adhesive layer 6 is shown. Sometimes, a decorative sheet having a concave pattern may be formed by using an embossed plate from the surface protective layer 5 side, for example, a laminated sheet formed with a concave pattern made of a conduit groove.

  Next, the present invention will be described in more detail with reference to the following examples. The scope of the present invention is not limited to the examples.

  As a curing agent, acrylic / urethane block copolymer is used as the main agent on the entire surface of one side of a 120 μm thick transparent polypropylene film [Mitsubishi Chemical MKV Co., Ltd .: PC008 (trade name)] with corona discharge treatment on both sides. A 2 μm thick transparent primer layer made of a two-component curable urethane resin to which isocyanate is added is formed on the other surface by a gravure printing method, and then the transparent primer layer surface. In addition, 100 parts by weight of a transparent printing ink using a polyester urethane resin having a number average molecular weight of 10,000 and a glass transition temperature (Tg) of −40.0 ° C. as a vehicle, 5 parts by weight of silica particles having an average particle system of 4 μm. Using the blended printing ink composition, the gravure printing method is used to create a conduit pattern layer (pattern-like After forming the printing layer, 16 parts by weight of silica coated with a silicone oil on the entire surface on which the conduit pattern layer is formed with 100 parts by weight of an ionizing radiation curable resin composition (urethane acrylate ionizing radiation curable resin) And a transparent surface protection of 5 μm thickness by applying an electron beam (acceleration voltage: 125 KeV, irradiation amount: 5 Mrad) and applying a benzotriazole UV absorber and a hindered amine radical scavenger. The intermediate sheet on which the layer is formed is a 0.3 mm-thick projecting plate (saddle material) in which a backing paper (paper-reinforced paper 23 g / m 2 / PE 25 μm / paper-reinforced paper 30 g / m 2) is attached on one side in advance. On the other side, an emulsion type adhesive [manufactured by Chuo Rika Co., Ltd .: BA-11B (5 parts by weight) is added to Rikabond BA-10L (100 parts by weight)] The adhesive sheet of the present invention was prepared by laminating with a roll laminator machine so that the transparent surface protective layer was exposed via a 6 g / scale 2 coating in a wet state. Next, after applying and drying 8 g / sq. 2 of vinyl acetate adhesive on a 3 mm thick MDF on the decorative sheet in a wet state, a roll laminator machine is used so that the backing sheet of the decorative sheet is positioned on the coated surface. An attached decorative board of the present invention was prepared.

  About the decorative board of Example 1 produced above, stain resistance, abrasion resistance, and gloss were evaluated by the evaluation methods described below, and the results are summarized in Table 1.

〔Evaluation methods〕
・ Contamination resistance:
According to the JAS Plywood Contamination A test, specifically, the decorative board was cut to a 10 cm square to make a test piece, which was placed horizontally and then placed on the surface protective layer surface of the test piece. A black ink (as defined in JIS S 6037 marking pen) and a red crayon (as defined in JIS S 6026) were each drawn 10 cm wide and 10 cm long straight lines, allowed to stand for 4 hours, and then impregnated with ethanol When the straight line having a length of 10 cm was wiped off, it was shown as “good” by ◯ and when it was not wiped, it was shown as “bad” by evaluation.
・ Abrasion resistance:
Steel wool (# 0000) was attached to a weight adjusted to a load of 29.4 kPa (300 g / cm 2), the surface of the decorative sheet was rubbed 20 times, and the surface change was visually evaluated according to the following evaluation criteria.
(Evaluation Criteria)-A case where no surface change was observed at all was indicated as good by a circle, and a case where a surface change was clearly recognized was indicated by a failure as indicated by a cross.
・ Gloss evaluation:
Using a gloss meter (Murakami Color Research Laboratory product: GMX-203 (trade name)) under a condition of an incident angle of 60 degrees, a low gloss region (conduit pattern layer region) and a high gloss region (region other than the conduit pattern layer) ) Gloss value was measured. The higher the number, the higher the gloss (high gloss), and the lower the number, the lower the gloss (low gloss).

  As is clear from Table 1, the decorative sheet of the present invention and the decorative board using the decorative sheet have a natural texture unique to natural wood, using the bark and terry peculiar to the veneer as they are, similar to the veneer decorative board. Design that has a sense of depth (depth) that cannot be expressed with a veneer decorative board, because the conduit pattern layer is arranged via a veneer and a transparent polypropylene film. In addition to being able to express the effect, it is also possible to recognize this area (area of the conduit pattern layer) as a low-gloss area by forming a conduit pattern layer, and other areas (conduit pattern) A region other than the layer) can be recognized as a high gloss region as a convex portion, and a design effect with a visually uneven feeling can be expressed, and a new design effect is exhibited.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Propylene-based sheet layer 3 Primer layer 4 Pattern-like low gloss printing layer 5 Surface protective layer 6 Adhesive layer 7 Veneer

In order to achieve the above object, the present inventor provides a decorative low gloss printed layer on one side of a transparent or translucent non-colored propylene-based sheet layer. further transparent surface protective layer comprising a cured resin on the entire surface one surface of the propylene sheet layer provided with the patterned low gloss print layer after providing the transparent surface protecting the propylene sheet layer It is laminated on one surface of the projecting plate so that the layer is exposed, and embossing is formed from the transparent surface protective layer side .

The present invention according to claim 2 is the decorative sheet according to claim 1, wherein the curable resin is an ionizing radiation curable resin .

The present invention according to claim 3 is the decorative sheet according to claim 1 or 2 , wherein a backing paper is laminated on the other surface of the protruding plate .

Further, the present invention according to claim 4 is the decorative sheet according to any one of claims 1 to 3, wherein, in each layer constituting the decorative sheet, at least the transparent surface protective layer constituting the exposed surface or The propylene-based sheet layer contains at least an ultraviolet absorber .

The present invention according to claim 5 is characterized in that the decorative sheet according to any one of claims 1 to 4 is pasted with a base material for decorative plate through an adhesive layer .

Claims (6)

Laminate a propylene-based sheet layer having a surface-protective layer on one side of the veneer after a patterned low-gloss printing layer is provided on one side so that the surface-protective layer is exposed. A decorative sheet characterized by comprising The decorative sheet according to claim 1, wherein the surface protective layer is made of a curable resin. The decorative sheet according to claim 2, wherein the curable resin is an ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 3, wherein a backing paper is laminated on the other surface of the protruding plate. 5. The ultraviolet absorber is contained in at least the propylene-based sheet layer or the surface protective layer constituting at least the exposed surface among the layers constituting the decorative sheet. The decorative sheet described in 1. A decorative board, wherein the decorative sheet according to any one of claims 1 to 5 is bonded to a decorative sheet base material through an adhesive layer.

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