KR101456731B1 - Decorative sheet and decorative plate using the decorative sheet - Google Patents

Abstract

A decorative sheet formed by laminating a propylene-based sheet layer on one surface of a veneer having a concave surface and a surface protective layer formed on the entire surface thereof so as to expose the surface protective layer; and a decorative sheet, Wherein the propylene-based sheet layer having the surface protective layer formed on the entire surface of the surface on which the print layer is formed is laminated so that the surface protective layer is exposed. It is an object of the present invention to provide a decorative sheet which does not deteriorate the bark and luster of the veneer board but which has both visual depth and irregularity as a design and also has excellent stain resistance and abrasion resistance and a decorative sheet using the decorative sheet.

A veneer, a propylene-based sheet layer, a veneer sheet, a decorative sheet, a low-

Description

[0001] DESCRIPTION [0002] DECORATIVE SHEET AND DECORATIVE PLATE USING THE DECORATIVE SHEET [0003]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet made of a veneer for use in surface decoration such as a wall material, an operating material, a window, etc., and a decorative sheet laminated on the substrate.

Background Art [0002] Conventionally, there has been proposed a method of manufacturing a plywood, a particleboard, a high-density fiberboard (HDF), a medium-density fiberboard ( MDF), inorganic plates such as calcium silicate plate and gypsum board, and veneers made by slicing natural wood thinly on the surfaces of the above-mentioned substrates A veneer panel is widely used as an inexpensive and high-quality decorative plate compared to a non-natural wood material because it has approximately the same design characteristics as a non-natural wood material.

As a constitution of the veneer panel decorative panel, generally, the surface of a substrate such as a laminated board, a particle board, a high density fiberboard (HDF), a medium density fiber board (MDF) or the like, or an inorganic board such as a calcium silicate board or a gypsum board, And the surface of the veneer panel is coated as necessary. However, when the veneer panel is cracked due to changes in temperature or humidity of the four seasons (minute cracks generated by the grain) and the degree of cracking is large, And the clothes are caught and damaged by the contact of the veneer sheet. In addition, in recent years, in the situation where it is difficult to obtain a rare wood as a raw material of a veneer, the thickness of the veneer tends to be thinned to 0.1 to 0.3 mm, and the occurrence of cracking tends to increase.

As a method of improving such cracking, proposals have been made to improve an adhesive for bonding a substrate and a veneer (see, for example, Patent Documents 1 and 2). The technique disclosed in Patent Document 1 is intended to reduce the cracking due to the combination of the elastomer adhesive and the non-siding paper, and the technique disclosed in Patent Document 2 is a technique in which a polyvinyl alcohol aqueous solution and a carboxylated A main agent containing an essential synthetic rubber latex as a main component and a curing agent containing an isocyanate compound having two or more isocyanate groups in a molecule as essential components and adding water required for viscosity adjustment, The base material and the veneer plate are bonded to each other by using an adhesive composed of a composition, thereby preventing cracks and the like.

However, not only the above-mentioned problem, but also the problem that the veneer board is difficult to remove the contamination when the surface of the veneer board is stained, for example, in the case of a white veneer board such as cypress, It is impossible to maintain the original white tint and there is a problem that the high-quality image is damaged.

Patent Document 1: Japanese Patent Publication No. 58-56517

Patent Document 2: Japanese Patent Application Laid-Open No. 59-202801

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and has as its object to provide a veneer board which is free from damage to the bark and luster of the veneer board and which has both visual depth and irregularity as a design and has excellent stain resistance and abrasion resistance Sheet and a decorative sheet using the decorative sheet.

A decorative sheet of the present invention according to claim 1 of the present invention is characterized in that a propylene-based sheet layer having a surface protective layer formed on the entire surface of a surface having a concave shape is laminated on one surface of a veneer, And the like.

According to a second aspect of the present invention, in the decorative sheet according to the first aspect, a pattern low-gloss printing layer is formed between the propylene-based sheet layer and the surface protection layer.

According to a third aspect of the present invention, there is provided a pressure-sensitive adhesive sheet comprising a surface layer on which a patterned low-gloss printing layer is formed and a surface protective layer formed on one surface of the veneer, .

According to a fourth aspect of the present invention, in the decorative sheet according to any one of the first to third aspects, the surface protection layer is made of a curable resin.

According to a fifth aspect of the present invention, in the decorative sheet according to the fourth aspect, the curable resin is an ionizing radiation curable resin.

According to a sixth aspect of the present invention, in the decorative sheet according to any one of the first to fifth aspects, a papermaking paper is laminated on the other surface of the veneer.

According to a seventh aspect of the present invention, in the decorative sheet according to any one of the first to sixth aspects, at least the propylene-based sheet layer or the surface protective layer constituting the light- At least an ultraviolet absorber is contained.

The decorative sheet of the present invention described in claim 8 is obtained by adhering the decorative sheet according to any one of claims 1 to 7 to a base material for an image forming plate through an adhesive layer.

The decorative sheet of the present invention and the decorative sheet using it can express the natural texture unique to the natural wood by utilizing the bark and luster of the veneer as they are and can form a concave shape in the propylene-based sheet layer, By forming a layer, it is possible to express a design effect with a sense of depth and irregularity visually, and at the same time an effect of excellent stain resistance and abrasion resistance is exhibited.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a layer diagram showing a first embodiment of a decorative sheet according to the present invention. FIG.

Fig. 2 is a layer diagram showing a second embodiment of the decorative sheet according to the present invention. Fig.

Fig. 3 is a layer diagram showing the third embodiment of the decorative sheet according to the present invention. Fig.

[Description of Symbols]

1, 10, 20: Facial sheet

2, 12: Propylene-based sheet layer

3, 13: primer layer

4, 14: pattern-shaped low-gloss printing layer

5, 15: surface protective layer

6: Concave

7: Adhesive layer

8: Veneers

The present invention will be described in detail below with reference to the drawings.

Fig. 1 is a layer diagram showing a first embodiment of a decorative sheet according to the present invention, Fig. 2 is a layer diagram showing a second embodiment of a decorative sheet according to the present invention, 1, 10 and 20 are a decorative sheet, 2 and 12 are a propylene-based sheet layer, 3 and 13 are primer layers, 4 and 5 are a base layer, 14 a low-gloss print layer, 5, 15 a surface protective layer, 6 a concave shape, 7 an adhesive layer, and 8 a veneer.

Fig. 1 is a sectional view showing the first embodiment of the decorative sheet according to the present invention. Fig. 1 is a view showing the decorative sheet according to the first embodiment of the present invention. Fig. (3) is formed on the entire surface of the primer layer (3), a surface protective layer (5) is formed on the entire surface of the primer layer (3), and a polyol component and an isocyanate Curing type urethane-based adhesive composed of the component (A) and the adhesive layer (B).

With this configuration, the veneer board 8 and the concave shape 6 are disposed with the propylene-based sheet layer 2 therebetween, so that the design effect with depth (depth) can be expressed.

Fig. 2 is a view showing the layer structure of the decorative sheet according to the present invention. Fig. 2 is a view showing the layer structure of the decorative sheet according to the second embodiment of the present invention. And the layer 4 is formed. The rest is the same as the cosmetic sheet 1 of the first embodiment.

By such a constitution, in addition to the effect of the first embodiment, the portion of the pattern-like low-gloss printing layer 4 can be visually recognized as the concave portion, so that the design effect with irregularity can be expressed. 1 and 2, as the concave shape 6 formed in the propylene-based sheet layer 2, a conduit groove is suitable.

FIG. 3 is a view showing the layer structure of the decorative sheet according to the third embodiment of the present invention. FIG. 3 is a view showing the layer structure of the decorative sheet according to the third embodiment of the present invention, The propylene-based sheet layer 12 in which the surface protective layer 15 is formed on the entire surface of the one surface on which the pattern-like low gloss printing layer 14 is formed on the surface of the veneer 7 Curable urethane-based adhesive composed of a polyol component and an isocyanate component, on one side of an adhesive layer (not shown).

With such a configuration, the veneer sheet 8 and the patterned low-gloss printing layer 14 are disposed with the propylene-based sheet layer 12 therebetween, so that the design effect with a depth feeling (depth) can be expressed. Furthermore, in this case, the portion of the pattern-like low-gloss printing layer 14 is visually perceived as a concave portion, so that the design effect with irregularity can be expressed. In Fig. 3, the pattern-like low-gloss printing layer 14 is a conduit pattern printing layer.

Next, all the materials constituting the decorative sheets (1, 10, 20) will be described. First, the propylene-based sheet layers 2 and 12 will be described.

The propylene-based sheet layers (2, 12) include homopolypropylene formed by homopolymerization of propylene, propylene-based sheets composed of a random copolymer or a block copolymer of two or three atoms copolymerized with ethylene, butene and the like , The propylene-based sheet layers 2 and 12 are those which do not damage the bark and luster of the veneer board 8, and transparent or semitransparent colored sheets are suitable. In the concave shape 6 according to the first and second embodiments, the chill roll when the propylene-based sheet is manufactured by the T-die extruder is embossed so that concave shape 6 is formed simultaneously with sheeting The formed propylene-based sheet can be produced. In the case of the third embodiment, a flat plate-like propylene-based sheet may be used as it is. In any case, the thickness of the propylene-based sheet is usually in the range of 60 to 120 占 퐉, and any state may be used in the unstretched state or in the uniaxially or biaxially stretched state. When the thickness is less than 60 占 퐉, there is a risk of heat wrinkling due to drying at the time of forming the primer layers 3, 13 and the surface protective layers 5, 15 or heat at the time of electron beam irradiation. A remarkable effect can not be expected in the effect. In addition, the propylene-based sheet may be subjected to a known reverse adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment or the like, if necessary. The propylene-based sheet may be appropriately added with known additives such as an antioxidant, a light stabilizer, and an ultraviolet ray inhibitor.

Next, the pattern low gloss printing layers 4 and 14 will be described. The patterned low-gloss print layer (4, 14) is a region (low-gloss region) where the region in which this layer is formed becomes lower in brightness than the other regions. Although this mechanism has not yet been fully elucidated, when unfired products of the surface protective layers 5, 15 made of the pattern-like low-gloss printing layer 4, 14 and the curable resin provided on the surface are coated, The resin component of the pattern-shaped low-gloss printing layer 4, 14 and the uncured resin of the surface protective layer 5, 15 partially interact with each other such as elution, dispersion and mixing by the combination of the respective materials or the selection of the coating conditions It is presumed that this is caused by expression. That is, the respective resin components in the ink of the pattern-shaped low-gloss printing layer 4, 14 and the uncured resin of the curable resin forming the surface protective layer 5, 15 are not completely in a commercial state in a short period of time Is in a suspended state and is present on or in the vicinity of the patterned low-gloss printing layer (4, 14), and the suspended portion is considered to be a low-gloss region by scattering light. The surface protective layer 5 or 15 is formed by crosslinking and curing in the state of having the suspended state so that the area on the patterned low gloss printing layer 4 or 14 in the surface protective layer 5 or 15 is at least the low- And it is presumed that the area is recognized as a concave part by the illusion of the eye. Depending on the kind of the curable resin composition for forming the patterned low-gloss printing layers 4 and 14 and the surface protective layers 5 and 15 and the coating conditions, the surface protective layers 5 and 15 ) May bulge along with the formation of the pattern-like low-gloss printing layers 4 and 14 to form a convex shape. Since the surfaces of the surface protective layers 5 and 15 have such a convex shape, light is scattered even in this portion, so that a more visual irregularity is emphasized, which is preferable. The height of the convex shape is desirably a height in a range in which the effect of the present invention is exhibited, and is usually in the range of 2 to 3 mu m.

The ink forming the patterned low gloss printing layers 4 and 14 has a property of causing interaction with the curable resin composition forming the surface protective layers 5 and 15 (uncured resin of the curable resin) And is appropriately selected in relation to the resin composition (uncured resin of the curable resin). Specifically, it is preferable that the vehicle of the ink contains urethane resin or polyvinyl acetal resin in an amount of 50% by weight or more. As the polyol component, the urethane-based resin may contain, as an isocyanate component, a polyol component such as an acryl polyol, a polyester polyol and a polyether polyol, an aromatic isocyanate such as tolylene diisocyanate, xylene diisocyanate and diphenylmethane diisocyanate, , Urethane resin (which may be linearly crosslinked or crosslinked in a mesh form) obtained by reacting an isocyanate such as aliphatic or alicyclic isocyanate such as hexamethylene diisocyanate and hydrogenated tolylene diisocyanate have. The polyvinyl acetal resin can be obtained by condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of the polyvinyl acetal resin include polyvinyl formal (formal resin), polyvinylacetacetal, polyvinyl propiolate, polyvinyl butyral (butyral resin), polyvinyl hexyl and the like.

In order to adjust the degree of the expression of the low-gloss region and the contrast of the gloss difference between the low-gloss region and the periphery thereof as necessary, it is preferable to use a resin composition such as an unsaturated polyester resin, an acrylic resin or a vinyl chloride- May be mixed and used. The mixing ratio of the gloss-adjusting resin ranges from 10 to 90% by weight based on the total amount of the vehicle. Within this range, sufficient enhancing effect of low-gloss region expression can be obtained. The ink for forming the patterned low-gloss printing layers 4 and 14 may be either uncolored or colored by adding a coloring agent such as a pigment. However, by coloring by the pigment, the concave is more clearly defined, It is possible to obtain a decorative sheet exhibiting excellent design effects in the depth and depth of recesses and protrusions.

In the present invention, when the pattern-like low-gloss print layer (4, 14) is formed, the surface protective layer (5, 15) is formed on the pattern low-gloss print layer The interaction between the ink constituting the low gloss printing layers 4 and 14 and the curing resin composition (uncured resin of the curing resin) constituting the surface protective layers 5 and 15 causes the pattern low gloss printing layer 4 , And 14 is at least a low-gloss region, and the region is recognized as a concave portion by an illusion of the eye. The film thickness of the patterned low-gloss printing layer (4, 14) is preferably 0.5 m or more and 5.0 m or less in consideration of printing suitability and interaction with the curable resin composition (uncured resin of the curable resin).

In addition, it is preferable to blend an extender pigment as fine particles in the printing ink for forming the patterned low-gloss printing layer (4, 14). By blending the extender pigment, scattering of light is 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. Of these, silica is preferred because it is a material having high flexibility in material design such as suction induction, particle diameter and pore volume, and excellent in designability, whiteness, and coating stability as an ink. Silica of fine powder is particularly preferable.

The average particle diameter of the silica is preferably larger than the film thickness (占 퐉) of the patterned low-gloss printing layer 4 and is usually 1.0 占 퐉 or more and the maximum particle diameter is the film thickness of the surface protective layers 5, The thicknesses of the surface protective layers 5 and 15 are usually not more than 10.0 占 퐉, preferably not more than 7.0 占 퐉, in consideration of all the physical properties required for the decorative sheet (post-processing aptitude and suitability when used) Mu m or less, and an optimum range of the average particle diameter is 2.0 mu m or more and 4.0 mu m or less. The amount of the extender pigment to be added to the ink for forming the patterned low-gloss printing layer 4 is suitably 5 to 15 parts by weight relative to 100 parts by weight of the ink composition other than the extender pigment. When the amount is less than 5 parts by weight, sufficient thixotropic property can not be imparted to the printing ink composition for forming the patterned low gloss printing layer 4, and when the amount is more than 15 parts by weight, the effect of imparting low gloss is lowered . In the present invention, the pattern-like low-gloss printing layer 4 is preferably a cardboard pattern printing layer.

Next, the surface protective layers 5 and 15 will be described. The surface protective layers 5 and 15 are made of the same materials as those of the decorative sheets 1, 10 and 20 (see Figs. 1 and 2 and Fig. 3), such as surface abrasion resistance, abrasion resistance, stain resistance, water resistance, The thickness is preferably from 1 to 20 mu m, and when the thickness is within this range, the film is broken when bending is performed, and whitening does not occur.

As the resin for forming the surface protective layers 5 and 15, it is appropriate to use a curable resin such as a thermosetting resin or an ionizing radiation curable resin, but more preferably, it has a hard surface hardness and excellent productivity Ionizing radiation-curable resin.

As the thermosetting resin, an unsaturated polyester resin, a polyurethane resin (including a two-liquid curing type polyurethane), an epoxy resin, an amino alkyd resin, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, - urea co-condensed resin, a silicon resin, and a polysiloxane resin. If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, or a polymerization accelerator is added to the resin. For example, an isocyanate or an organic sulfonic acid salt is added to an unsaturated polyester resin, a polyurethane resin or the like, and an organic amine or the like is added to the epoxy resin, and a peroxide such as methyl ethyl ketone peroxide or an azoisobutyl nitrile Are added to the unsaturated polyester resin. Examples of the method of forming the surface protective layer with the thermosetting resin include a method of dissolving the thermosetting resin described above and applying it by a known coating method such as a roll coating method or a gravure coating method, can do. The coating amount of the surface protective layer is suitably in the range of 1 to 20 g / m 2 as solid content, and particularly when the patterned low-gloss printing layer is formed, the film thickness is 0.5 탆 or more and 5.0 탆 or less and the average particle diameter of the fine particles is 1.0 to 7.0 Mu m, a solid content of 2 to 10 g / m < 2 > is suitable.

Next, the ionizing radiation curable resin will be described. The ionizing radiation curable resin is a resin which undergoes crosslinking polymerization reaction by irradiation with ionizing radiation and changes into a three-dimensional polymer structure. The ionizing radiation means having energy capable of polymerizing and crosslinking molecules in an electromagnetic wave or a charged particle beam and includes visible rays, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X rays, electron rays and ion rays. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light source, a light source such as ultra high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, black light fluorescent lamp, metal halide lamp and the like can be used. As the wavelength of ultraviolet rays, 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 Bandegraph type, a resonant transformer type, an insulating core transformer type, or a linear type, a dynamictron type, and a high frequency type can be used. As the electron beam to be used, those having 100 to 1000 keV, preferably 100 to 300 keV are used. The dose of the electron beam is usually about 2 to 15 Mrad.

Examples of the ionizing radiation curable resin include monomers, prepolymers, or polymers having a cationically polymerizable functional group such as a radically polymerizable unsaturated group such as a (meth) acryloyl group, a (meth) acryloyloxy group, or an epoxy group in the molecule. These monomers, prepolymers or polymers may be used singly or in combination of plural kinds. In the present specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The term "ionizing radiation" means having an energy capable of polymerizing or crosslinking a molecule in an electromagnetic wave or a charged particle beam, and is usually ultraviolet ray or 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 Ralidon, and the like. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10000, the surface properties of the cured resin layer such as abrasion resistance, abrasion resistance, chemical resistance and heat resistance are insufficient. The above-mentioned acrylate and methacrylate can be used in common, but acrylate is faster in terms of crosslinking curing speed in ionizing radiation, and therefore acrylate is advantageous for the purpose of efficiently curing at high speed in a short time.

Examples of the prepolymer having a cationic polymerizable functional group include epoxy resins such as bisphenol epoxy resin, novolac epoxy resin and alicyclic epoxy resin, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, ester vinyl ethers, A vinyl ether resin, a cyclic ether compound, a spiro compound, and the like.

Examples of monomers having a radically polymerizable unsaturated group include mono (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl (meth) acrylate (Meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, methoxybutyl Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, (Meth) acrylate, isobornyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol , Methoxypropylene glycol Glycol (meth) acrylate, and the like can be mentioned 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl hydrogen propyl terephthalate.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di Acrylate, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acryloyloxyethyl phosphate, glycerin polyethylene oxide tri (meth) acrylate, and tris (meth) acryloyloxyethyl phosphate.

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

When the above ionizing radiation curable resin is cured by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. The photopolymerization initiator in the case of a resin system having a radical polymerizable unsaturated group may be at least one selected from the group consisting of acetophenones, benzophenones, thioxanthones, benzoins, benzoins, benzoin methyl ethers, heilabenzoyl benzoates, , Dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, isopropyl-N, N-dimethylaminobenzoate, and the like can be used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a prilloxanodinium dialyl iodide salt and the like may be used alone or as a mixture. The amount of these photopolymerization initiators to be added is generally about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation curable resin. The application method and application amount of the ionizing radiation curable resin are the same as those of the thermosetting resin, and a description thereof will be omitted.

In the case where the surface protection layers 5 and 15 are further imparted with abrasion resistance and abrasion resistance, fine particles such as? -Alumina, silica, kaolinite, iron oxide, diamond and silicon carbide . The particle shape may be a spherical shape, an elliptical shape, a multi-sided shape, a scaly shape or the like, and is not particularly limited, but a spherical shape is preferable. Examples of the organic material include synthetic resin beads such as crosslinked acrylic resin and polycarbonate resin. The particle diameter is usually about 3 to 200% of the film thickness. Of these, spherical a-alumina is particularly preferable in that it has a high hardness and a large effect on improvement of abrasion resistance, and it is relatively easy to obtain spherical particles. The mixing ratio of the fine particles to the curable resin forming the surface protective layer 5 is 1 to 80 parts by weight based on 100 parts by weight of the curable resin.

Next, the primer layers 3 and 13 will be described. The primer layers 3 and 13 may be formed for the purpose of improving adhesion strength between the propylene-based sheet layers 2 and 12 and the patterned low-gloss printing layers 4 and 14 or the surface protection layers 5 and 15 Lt; / RTI > Examples of the resin used for the primer layers 3 and 13 include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins and nitrocellulose resins. The resin may be used alone or in combination as a coating composition or an ink composition and may be formed using a suitable coating means such as a roll coating method or a gravure printing method.

However, it is particularly preferable that the primer layers (3, 13) are formed of (i) a copolymer of an acrylic resin and a urethane resin, and (ii) a resin comprising isocyanate. That is, the copolymer of the acrylic resin and the urethane resin of (i) contains an acrylic polymer component having a hydroxyl group at the terminal (component A), a polyester polyol component having a hydroxyl group at both terminals (component B), a diisocyanate component (Component D) such as a diamine is added to the prepolymer, and the chain is elongated. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acryl-polyester urethane copolymer having a hydroxyl group at the terminal. And reacting the hydroxyl group at the terminal of the acryl-polyester urethane copolymer with the isocyanate of (ii) to cure the acryl-polyester urethane copolymer.

As the component A, a straight chain acrylic ester polymer having a hydroxyl group at the terminal is used. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferred because it is excellent in weather resistance (in particular, the property against photodegradation) and is easily copolymerized with urethane to compatibilize Do. The component A is an acrylic resin component in the copolymer and preferably has a molecular weight of 5,000 to 7,000 (weight average molecular weight), because it is excellent in weatherability and adhesiveness. The component A may be a compound having a hydroxyl group at both ends, but it may be used in combination with a compound having a hydroxyl group at both ends, in which conjugated double bonds remain at one terminal. By mixing the acrylic polymer in which the conjugated double bonds remain, a conjugated double bond of the ionizing radiation curable resin of the layer in contact with the primer layer, for example, the surface protective layer (5, 15), reacts with the acrylic polymer, Can be improved.

The component B reacts with a diisocyanate to form a polyester urethane and constitutes a urethane resin component in the copolymer. The component B is a polyester diol having hydroxyl groups at both terminals. Examples of the polyester diol include an addition reaction product of a diol compound having an aromatic or spirocyclic skeleton with 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 And polyester compounds. Examples of the diols include short chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol and methylpentene diol, and alicyclic short chain diols such as 1,4-cyclohexanedimethanol. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, and terephthalic acid. Preferred as the polyester polyol is an adipic acid or a mixture of adipic acid and terephthalic acid, particularly adipic acid, as an acid component, and adipate-based polyol having 3-methylpentanediol and 1,4-cyclohexanedimethanol as a diol component, Ester.

The urethane resin component in the primer layer (3, 13), which is formed by reacting the component B with the component C, imparts flexibility to the primer layer (3, 13) 12). Further, the acrylic resin component composed of an acrylic polymer contributes to weather resistance and blocking resistance in the primer layers (3, 13). The molecular weight of the component B is not particularly limited as long as the urethane resin capable of sufficiently exhibiting flexibility can be obtained in the primer layer. A mixture of adipic acid or a mixture of adipic acid and terephthalic acid, 3-methylpentanediol and 1,4 -Cyclohexanedimethanol is preferably 500 to 5000 (weight average molecular weight).

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 di Isocyanate, 1,4'-cyclohexyldiisocyanate, and the like. As the diisocyanate component, isophorone diisocyanate is preferable because of excellent physical properties and cost. When the above-mentioned components A to C are reacted, the equivalent ratio of the hydroxyl group (which may be an amino group) to the total of the acrylic polymer, the polyester polyol and the chain extender described later and the isocyanate group causes the isocyanate group to be excessive.

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, A compound in which a diisocyanate is added to the hydroxyl group is also mixed to form a prepolymer in which excess isocyanate groups and hydroxyl groups remain. Adding an isocyanate group to the prepolymer as a chain extender such as isophoronediamine or hexamethylenediamine to react with the chain extender and introducing the acrylic polymer component into the molecule of the polyester urethane , An acrylic-polyester urethane copolymer (i) having a hydroxyl group at the terminal thereof can be obtained.

(ii) is added to the acrylic-polyester urethane copolymer of the present invention (i), and the coating liquid is adjusted to a necessary viscosity in consideration of the coating method and the coating amount after drying. The gravure coating method and the roll coating method And the primer layers 3 and 13 may be formed by applying them by a known coating method such as a coating method. The isocyanate of (ii) is not particularly limited as long as it is capable of reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (i) to effect crosslinking and curing. For example, aliphatic or aromatic isocyanates having two or more hydroxyl groups can be used, Aliphatic isocyanate is preferable in view of prevention of discoloration and weather resistance. Specific examples thereof include monomers of tolylene diisocyanate, xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or oligomers such as dimers and trimer thereof, And polyisocyanates such as derivatives in which a polyol is added (an adduct). The decorative sheets 1, 10 and 20 shown in Figs. 1 to 3 have the constitution in which the primer layer 3 is formed. However, this is a decorative sheet specification according to a demand of a high level, These primer layers 3 and 13 need not always be formed.

The coating amount after drying of the primer layer (3, 13) is 1 to 20 g / m 2, preferably 1 to 5 g / m 2. The primer layers 3 and 13 may be a layer to which additives such as a filler such as silica powder, a light stabilizer, and a coloring agent are added as needed.

Although not shown, the back surface of the propylene-based sheet layers 2 and 12 (the surface opposite to the surface on which the surface protective layers 5 and 15 are formed) shown in Figs. 1, 2 and 3, And the adhesive strength when the propylene-based sheet layers 2 and 12 and the veneer sheet 8 are laminated through the adhesive layer 7 to form the decorative sheets 1, 10, and 20 may be improved will be. The primer layer formed on the back surface of the propylene-based sheet layers (2, 12) can be appropriately formed if necessary in the case of insufficient adhesion. For the primer layer, for example, 3, and 13) may be appropriately selected and used.

The adhesive layer 7 may suitably be formed of, for example, a two-component curing type urethane adhesive composed of a polyol component and an isocyanate component. The adhesive layer 7 is formed between the propylene-based sheet layer 2 or 12 and the veneer 8 and is provided on the side where the propylene-based sheet layer 2 or 12 and the veneer 8 are laminated. .

As the polyol component and the isocyanate component of the two-liquid curing type urethane adhesive, the B component and the C component described in the polymer layer (3, 13) portion are used, respectively.

The veneers 8 are not particularly limited as long as the veneers 8 are formed by slicing natural wood into thin sheets. In the present invention, the veneers 8 are made of natural wood such as fines, cedar, cypress, pale, (Wooden logs) are suitable. The thickness of the veneer board 8 is suitably 0.1 to 0.5 mm.

Although not shown, it is possible to prevent cracking or the like, improve waterproofness, or improve the suitability of processing on the back surface of the veneer 8 (the surface opposite to the surface on which the propylene-based sheet layers 2 and 12 are formed) For the purpose of the present invention, a three-layer structure consisting of paper, interstice strengthening paper, resin impregnated paper, nonwoven fabric, woven fabric, or a combination of these three layers of polyethylene or polypropylene, for example, a ground reinforcing paper / polyethylene or polypropylene / Or a veneer having a laminated structure made of a plastic material such as a polyethylene / polypropylene / polypropylene / polypropylene / polypropylene / aluminum foil / polyethylene / polypropylene / aluminum foil / polyethylene / polypropylene / aluminum foil On one surface of an unoriented or stretched film such as a polyester film, a polyamide film, a polyolefin film, etc., a film of aluminum or silicon oxide , An aluminum oxide, an indium oxide, a tin oxide, or a zirconium oxide, or a vapor deposition film on which at least one side of the vapor deposition film is coated with paper, a ground reinforcing paper, a resin impregnated paper, a nonwoven fabric, It is also possible to use a veneer having a structure in which laminated superimposed paper is laminated with an adhesive.

Further, in the present invention, in order to use a veneer sheet obtained from a fibrillating material, a cedar wood material, a cypress wood material, or a pale and white natural wood (raw wood) as the veneer board 8, It is necessary to keep the original white color so as not to damage the high-quality image. The surface protective layer 5, 15, the pattern low gloss printing layer 4, 14, the primer layer 3, Based, benzophenone-based, triazine-based, benzophenone based, and benzophenone based on each layer located on the surface side of the veneer sheet 8, such as the above propylene-based sheet layers 13, 13, , Inorganic ultraviolet absorbents such as titanium dioxide, cerium oxide and zinc oxide having an average particle diameter of about 5 to 120 nm, known light stabilizers such as hindered amine type antistatic agents, leveling agents Well-known The propylene-based sheet layers 2, 12 or the surface protective layers 5, 15 constituting the surface of the decorative sheets 1, 10, 20 are preferably provided with the organic ultraviolet absorbing It is preferable to add a known additive such as an ultraviolet absorber.

Although not shown, examples of the adhesive used for the adhesive layer for adhering the decorative sheets 1, 10, and 20 and the base material for the veneer sheet through the adhesive layer include a thermoplastic resin type, a thermosetting type Any type of adhesive such as a resin system, a rubber (elastomer) system or the like may be used. These can be publicly known or commercially available products. Examples of the thermoplastic resin adhesives include polyvinyl acetate resins, polyvinyl alcohol, polyvinyl acetal (polyvinylformal, polyvinyl butyral, etc.), cyanoacrylates, polyvinyl alkyl ethers, polyvinyl chloride, polyamides, Examples of thermosetting resin-based adhesives include urea resins, melamine resins, phenolic resins, and resorcinol-based resins. Examples of the thermosetting resin-based adhesives include thermosetting resins such as methyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer and ethylene- Epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyamideimide, polyvinyl imidazole, polybenzothiazole, and the like. Examples of the rubber adhesives include natural rubber, regenerated rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, Block copolymer rubber (SBS, SIS, SEBS, etc.) and the like.

The base material (not shown) used for making the base material may be a wood base material such as a medium density fiberboard (MDF), a high density fiberboard (HDF), a particle board and a plywood, An inorganic base such as a calcium plate and a gypsum board, and a metal plate.

As for the thickness of the base material for a flat plate, 0.5 mm or more in thickness for a metal plate and 1.0 mm or more in other cases are suitable for practical use.

Hereinafter, 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.

(Embodiment 1)

(OW-E S-2 clear (trade name), manufactured by Riken Technos Co., Ltd.) having a concave shape made of a conduit groove on one side and a corona discharge treatment on both sides of a 100 μm thick transparent polypropylene film A urethane / nitrocellulose-based primer layer on the other side was laminated on the entire surface of the surface on which the acrylic / urethane block copolymer was formed, and a two-part curing type urethane-based resin having isocyanate added as a curing agent, Layer was formed by gravure printing, and then an ionizing radiation curable resin composition (16 parts by weight of silica coated with silicone oil per 100 parts by weight of urethane acrylate based ionizing radiation curable resin) was added to the entire surface of the transparent primer layer side At the same time, a benzotriazole-based ultraviolet absorber and a hindered amine radical scavenger (An accelerating voltage of 125 KeV and an irradiation dose of 5 Mrad) was irradiated to an intermediate sheet on which a transparent surface protective layer having a thickness of 5 μm was formed, (Rikabond BA-10L (100 parts by weight) manufactured by Juurica Kabushiki Kaisha) was applied on the other side of a 0.3 mm thick veneer board (5 parts by weight) was coated with 6 g / chuck ² (? 65.35 g / m < 2 > under wet condition) to form a transparent surface protective layer. A decorative sheet corresponding to the shape was produced. Subsequently, the decorative sheet was coated with MDF having a thickness of 3 mm in a wet state at 8 g / chuck ² (≒ 87.14 g / m 2) and dried. Thereafter, a roll laminator To thereby produce an encapsulant of the invention.

(Second Embodiment)

(Made by Riken Technos Co., Ltd.: OW-E S-2 clear (trade name)] having a concave shape made of a conduit groove on one side and a corona discharge treatment on both sides A 2 μm thick transparent primer layer made of a two-component curing type urethane resin with an acrylic / urethane block copolymer as a main component and an isocyanate added as a curing agent was applied on the entire surface of the provided surface, and a urethane / nitrocellulose primer layer Were each formed by a gravure printing method and then 100 parts by weight of a transparent printing ink having a polyester-based urethane resin as a vehicle having a number average molecular weight of 10,000 and a glass transition temperature (Tg) of -40.0 DEG C was placed on the surface of the transparent primer layer , And 5 parts by weight of silica particles having an average particle size of 4 mu m were blended, After forming a pattern layer (a pattern layer low-gloss layer in the present invention), an ionizing radiation curable resin composition (containing 100 parts by weight of a urethane acrylate ionizing radiation curable resin as a silicone oil (Accelerating voltage: 125 KeV, irradiation dose: 5 Mrad) was irradiated while applying a surface-coated silica (16 parts by weight) and a benzotriazole-based ultraviolet absorber and a hindered amine radical scavenger added thereto. The intermediate sheet on which the transparency surface protective layer was formed was laminated on the other surface of a veneer board (cypress wood) having a thickness of 0.3 mm and adhered to one side in advance by an insert paper (abrasive reinforcing paper 23 g / m 2 / PE 25 m / ground reinforcing paper 30 g / manufactured side emulsion type adhesive to the surface [juice ohrikka whether or sikki claim: Rika bond BA-10L (100 parts by weight) BA-11B (5 parts by weight) to 6g / chuck the added adhesive in the wet state ² (≒ 65.35g for / M 2). The decorative sheet corresponding to the second embodiment of the present invention was produced by laminating the transparent decorative sheet with a roll laminator so that the transparent surface protective layer was exposed. After the base adhesive was applied and dried at 8 g / chuck ² (≒ 87.14 g / m 2) in a wet state, the colored plate of the present invention adhered with a roll laminator was placed on the coated surface so that the superfine paper of the decorative sheet was positioned.

(Third Embodiment)

On one side of a 120 μm thick transparent polypropylene film (PC008 (trade name) manufactured by Mitsubishi Chemical Corporation, Mitsubishi Kagaku KK) subjected to corona discharge treatment on both sides, an acrylic / urethane block copolymer was used as a main component and an isocyanate A urethane / nitrocellulose primer layer was formed on the other side by a gravure printing method, and then a number average of a number average A printing ink composition was prepared by blending 100 parts by weight of a transparent printing ink having a molecular weight of 10,000 and a polyester-based urethane resin having a glass transition temperature (Tg) of -40.0 DEG C as a vehicle and 5 parts by weight of silica particles having an average particle size of 4 mu m After forming a conduit pattern layer (pattern-shaped low-gloss printing layer according to the present invention) by gravure printing, 16 parts by weight of silica coated on a surface of silicone resin with 100 parts by weight of a urethane acrylate ionizing radiation curable resin was blended with the ionizing radiation curable resin composition on the entire surface of the surface on which the conduit pattern layer was formed and a benzotriazole ultraviolet absorber and a hindered (Accelerating voltage: 125 KeV, irradiation amount: 5 Mrad) was applied to the surface of the intermediate sheet on which a transparent surface protective layer having a thickness of 5 탆 was formed, (Rikabond BA-1 manufactured by Juroric Kagaku Co., Ltd.) was applied to the other side of a 0.3 mm thick veneer board (cypress wood) to which the reinforcing base material 23 g / m 2 / PE 25 m / ground reinforcing paper 30 g / 10L (100 parts by weight) to the BA-11B (5 parts by weight) to 6g / chuck the added adhesive in the wet state ² (≒ 65.35g / ㎡) applying] the transparent surface protective layer is exposed through a roll laminator so that the group for The of the present invention by laminating the decorative sheet was produced which corresponds to the third embodiment. Subsequently, the decorative sheet was coated with a vinyl acetate-based adhesive in a wet state at 8 g / chuck ² (≒ 87.14 g / m 2) on MDF having a thickness of 3 mm and dried, and then the roll laminator Thereby producing a colored plate of the present invention adhered with a base.

The colored panels of the first, second, and third embodiments fabricated above were evaluated by an evaluation method for evaluating stain resistance, abrasion resistance, and gloss, and the results are summarized in Table 1.

[Assessment Methods]

ㆍ Stain resistance:

Specifically, in accordance with the JAS plywood contamination A test, the lacquer plate was cut into a square having a side of 10 cm as a test piece. The test piece was placed horizontally on the surface protective layer of the test piece, and then a commercially available blue ink for office use, (Defined by JIS S 6037 marking pen) and a red crayon (defined by JIS S 6026), a straight line having a length of 10 cm and a width of 10 mm was left for 4 hours and then wiped with a cloth impregnated with ethanol, A straight line having a length of 10 cm was wiped off and evaluated as good, and those not wiped off were evaluated as bad and evaluated as x.

ㆍ Abrasion resistance:

The surface of the decorative sheet was rubbed 20 times with a steel wool (# 0000) attached to a weight adjusted to have a load of 29.4 kg (300 g / cm 2), and the surface change was visually evaluated with the following evaluation criteria.

(Evaluation Criteria) - Those in which no change in surface was observed at all were evaluated as good, and those in which the surface change was clearly identified were evaluated as bad and evaluated as x.

ㆍ Evaluation of gloss:

(Area other than the conduit pattern layer) in the low-gloss area (area of the conduit pattern layer) and the high-gloss area (area other than the conduit pattern layer) under the condition of an angle of incidence of 60 degrees using a gloss meter (product of Murakami Shikisai Co., Ltd., GMX- Was measured. The higher the number, the higher the gloss. The lower the number, the lower the gloss.

As is clear from Table 1, the decorative sheet of the present invention and the decorative sheet using the decorative sheet of the present invention can express the natural texture unique to the natural wood by utilizing the bark and luster unique to the veneer, Or the conduit groove and the conduit pattern layer are disposed between the veneer plate and the transparent polypropylene-based sheet, it is possible to express a design effect with a visual depth (depth) which can not be expressed by the veneer board, In addition, by forming a conduit pattern layer, it is possible to recognize this region (region of the conduit pattern layer) as a low-gloss region as a concave portion, and other regions (regions other than the conduit pattern layer) It can be recognized as a convex portion, and it is possible to express a design effect with a visual sense of unevenness. To exert the most effective.

The decorative sheet and the decorative sheet including the veneer of the present invention can be used for decorating furniture and furniture such as wall surfaces, operating materials, windows, and the like.

Claims (8)

A propylene-based sheet layer having a surface protective layer formed on one surface of the veneer and having a concave surface formed on the entire surface thereof is laminated so that the surface protective layer is exposed, and the propylene-based sheet layer and the surface protective layer Characterized in that the patterned low-gloss printing layer comprises an extender pigment and the average particle diameter of the extender pigment is larger than the thickness of the patterned low-gloss printing layer. . delete Wherein the propylene-based sheet layer on one surface of the veneer having the surface protective layer formed on the entire surface of the surface on which the patterned low-gloss printing layer is formed is laminated so as to expose the surface protective layer. The decorative sheet according to claim 1 or 3, wherein the surface protection layer is made of a curable resin. The decorative sheet according to claim 4, wherein the curable resin is an ionizing radiation curable resin. The decorative sheet according to any one of claims 1 to 3, further comprising laminated superimposed paper on the other side of the veneer. 4. The decorative sheet according to any one of claims 1 to 3, wherein at least the propylene-based sheet layer or the surface protection layer constituting at least the exposed surface among the layers constituting the decorative sheet contains at least an ultraviolet absorber. A veneer sheet characterized in that the decorative sheet according to any one of claims 1 to 3 is adhered to a base material for a veneer sheet with an adhesive layer therebetween.

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