JP2000025190A - Decorative laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the water resistance, contamination resistance, wear resistance or the like of a decorative laminated sheet and thereby facilitate the manufacture thereof by laminating an ionizing radiation-curable resin layer containing spherical alumina particles with a specified average particle dia, a decorative layer, a base sheet, an adhesive resin layer and an inorganic base layer in that order. SOLUTION: This decorative laminated sheet 1 is formed by laminating an ionizing radiation-curable resin layer 2, a decorative layer 3, a base sheet layer 4, an adhesive resin layer 5 and an inorganic base layer 6 in that order. The decorative layer 3 can be composed of a solid printed layer 3a formed by solid printing over the entire face and a pattern printed layer 3b formed by printing a pictorial pattern or the like on the surface of the solid printed layer 3a. The ionizing radiation-curable resin layer 2 contains spherical alumina particles with 3-50 μm average particle dia. and has a wear resistance on the outermost face of the decorative laminated sheet 1, serving as a surface resin layer for protecting the surface. The addition amount of the spherical alumina particles is set by adjusting a coating composition so that it is 5-20 pts.wt. to 100 pts.wt. ionizing radiation-curable resin component after curing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to floors, walls,
The present invention relates to a decorative material used as a surface decoration material for interiors such as ceilings, furniture, and various cabinets, and more particularly to a decorative plate using an inorganic base material used for applications requiring surface abrasion resistance.

[0002]

2. Description of the Related Art Conventionally, as a wall material for a kitchen or the like, a decorative plate formed by laminating decorative paper on the surface of an inorganic base material, a low-pressure melamine decorative plate, or the like has been used.

[0003]

However, a decorative board laminated with decorative paper is inferior in water resistance and stain resistance because the decorative paper is formed from a paper material. Had a problem. Further, the low-pressure melamine decorative board has good water resistance, stain resistance, and the like, but has a problem in that it requires a lot of trouble in production and has poor surface abrasion resistance.

The present invention has been made to solve the above-mentioned drawbacks of the prior art, and has as its object to provide a decorative board which is excellent in water resistance, stain resistance, abrasion resistance and the like and is easy to manufacture. I do.

[0005]

According to the present invention, there are provided (1) an ionizing radiation curable resin layer containing spherical alumina having an average particle diameter of 3 to 50 μm, a decorative layer, a substrate sheet layer, an adhesive resin layer, and an inorganic base. (2) the decorative sheet according to the above (1), wherein the adhesive sheet is impregnated in the base sheet layer and the inorganic base layer, and (3) the adhesive resin. Is a thermosetting resin, and is a decorative board according to the above (1) or (2).

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. As shown in FIG. 1, the decorative board 1 of the present invention is formed by laminating an ionizing radiation-curable resin layer 2, a decorative layer 3, a base sheet layer 4, an adhesive resin layer 5, and an inorganic base layer 6 in this order. ing. As shown in FIG. 1, the decorative layer 3 has a solid print layer 3a formed by solid printing on the entire surface, and a pattern print layer 3b formed by printing a pattern such as a pattern on the surface of the solid print layer.
And can be composed of In the figure, reference numeral 7 denotes a sealer layer. Hereinafter, each of the above layers will be described.

The ionizing radiation-curable resin layer 2 is a surface resin layer which contains spherical alumina having an average particle size of 3 to 50 μm, has abrasion resistance on the outermost surface of the decorative plate, and protects the surface. The spherical alumina used for the ionizing radiation-curable resin layer 2 may have a surface that is surrounded by a smooth curved surface, such as a true sphere, an ellipsoidal sphere obtained by flattening a sphere, and a shape close to the true sphere or the ellipsoidal sphere. I just need. The spherical alumina preferably has no protrusions or corners on the particle surface, and has no so-called cutting edge. Compared with amorphous alumina, spherical alumina greatly improves the wear resistance of the resin layer itself, does not wear the coating device, and does not wear other objects in contact with the coating film after curing. Further, there is a feature that the transparency of the coating film is increased, and the effect is particularly large when there is no cutting edge.

It is preferable that the coating composition is adjusted so that the spherical alumina is added in an amount of 5 to 20 parts by weight based on 100 parts by weight of the cured ionizing radiation-curable resin component. If the amount of spherical alumina is small, there is a possibility that effects such as improvement of abrasion resistance may not be sufficiently exhibited.On the other hand, if the amount of spherical alumina is too large, curing of the ionizing radiation-curable resin is impaired, and There are adverse effects such as the possibility that the flexibility of the film is reduced and the workability of the coating composition is reduced.

The spherical alumina includes α-alumina such as fused alumina and Bayer alumina, or a eutectic mixture of these with titania, zirconia and the like. As a method for making these alumina shapes spherical, a method in which pulverized amorphous alumina is put into a high-temperature furnace having a melting point or higher and melted, and then formed into a spherical shape using surface tension, or melted at a high temperature equal to or higher than the melting point A method of blowing out the mist into a mist to make it spherical.

[0010] Spherical α-alumina is disclosed in Japanese Unexamined Patent Publication No. 2-55.
No. 269, a mineralizer or crystallization agent such as alumina hydrate, a halogen compound or a boron compound is added to a pulverized product of fused alumina or sintered alumina in a small amount. By performing the heat treatment at a temperature for 2 hours or more, a cutting edge in alumina is reduced and, at the same time, a spherical shape is obtained. Such a spherical alumina is available from Showa Denko KK as "Spherical Alumina AS-10,
AS-20, AS-30, AS-40, and AS-50 "having various average particle diameters are commercially available.

[0011] Spherical alumina can treat the particle surface. For example, treatment with a fatty acid such as stearic acid improves dispersibility. In addition, by treating the surface with a silane coupling agent, the adhesion to the ionizing radiation-curable resin and the dispersibility of the particles in the coating composition are improved. Examples of the silane coupling agent include an alkoxysilane having a radically polymerizable unsaturated bond such as vinyl and methacryl in the molecule and an alkoxysilane having a functional group such as epoxy, amino and mercapto in the molecule. As the silane coupling agent, in the case of an ionizing radiation curable resin, it is preferable to use an alkoxysilane having a radical polymerizable unsaturated bond. Specific examples of the alkoxysilane having a radical polymerizable unsaturated bond include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, and γ-methacryloxypropyldimethylethoxy. Silane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ- Alkoxysilanes having radically polymerizable unsaturated bonds in molecules such as acryloxypropyldimethylethoxysilane and vinyltriethoxysilane, and functional groups such as epoxy, amino and mercapto in molecules There are alkoxysilanes having.

The method of treating the surface of the spherical alumina with a silane coupling agent is not particularly limited, and a known method can be used. For example, a method in which a predetermined amount of a silane coupling agent is sprayed while vigorously stirring spherical alumina as a dry method, or a method in which a predetermined amount of a silane coupling agent is dispersed after dispersing spherical alumina in a solvent such as toluene as a wet method. A method of adding and reacting is given. The amount (required amount) of the silane coupling agent to be applied to the spherical alumina is preferably such that the minimum coating area of the silane coupling agent is 10 or more with respect to the specific surface area of 100 of the spherical alumina. When the minimum coverage area of the spherical alumina is less than 10 with respect to the specific surface area of the spherical particles of 100, there is not much effect.

The particle diameter of the spherical alumina is usually from 5 to 100.
μm (average particle size) can be preferably used. If the average particle size of the spherical alumina is less than 5 μm, the coating may be opaque. On the other hand, if the average particle size exceeds 100 μm, the surface smoothness of the coating may be reduced. As the particle diameter of the spherical alumina decreases, the wear resistance decreases. On the other hand, when the particle diameter of the spherical alumina is large, the wear resistance is improved, but when it is too large, it becomes difficult to perform uniform coating at the time of coating. The relationship with the thickness particle diameter of the ionizing radiation-curable resin layer is as follows.

The average thickness of the ionizing radiation-curable resin layer is represented by t
(Μm) and the average particle diameter of the spherical alumina is d (μm), it is preferable that the following formula (1) is satisfied. When the average particle diameter d of the spherical alumina exceeds 2.0 t, the spherical alumina largely protrudes from the surface of the ionizing radiation-curable resin layer, and the appearance of the layer may be deteriorated. If the average particle diameter d of the spherical alumina is less than 0.3 t, there is a possibility that sufficient wear resistance may not be obtained.

[Formula 1] 0.3t ≦ d ≦ 2.0t (1)

The ionizing radiation-curable resin layer 2 may contain, in addition to the ionizing radiation-curable resin and spherical alumina, coloring agents such as dyes and pigments, fillers such as matting agents and extenders. it can.

The abrasion resistance of the ionizing radiation-curable resin used for the ionizing radiation-curable resin layer 2 improves as the crosslinking density increases. The crosslink density can be represented by, for example, the average molecular weight between crosslinks shown in the following formula (3). The average molecular weight between crosslinks is 1
It can be used in the range of 00 to 1000, preferably 100 to 700.

[0017]

## EQU2 ## Average molecular weight between crosslinks = total molecular weight / number of crosslink points (3) where the total molecular weight is Σ (the number of moles of each component × the molecular weight of each component). The number of points is {[{(the number of functional groups of each component −1) × 2} × the number of moles of each component].

The ionizing radiation-curable resin is, for example, a composition which is appropriately mixed with a prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or an epoxy group in a molecule, and which can be cured by ionizing radiation. Object is used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum that can polymerize or crosslink a molecule, and usually, an ultraviolet ray or an electron beam is used.

Examples of the above prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate and melamine methacrylate, polyester acrylates, and the like. Examples include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

The urethane acrylate includes, for example, a polyether-based urethane (meth) acrylate represented by the following general formula [1], which is obtained by reacting a polyether diol with a diisocyanate.

## STR1 ## ^{_{CH 2 = C (R 1)}} -COOCH 2 CH 2 -O
CONH-X-NHCOO - ^{[- CH (R 2) - (} CH 2) n -O- ] _m -CON
H—X—NHCOO—CH ₂ CH ₂ OCOC (R ¹ ) = CH ₂ (wherein R ¹ and R ² are each hydrogen or a methyl group, X is a diisocyanate residue, n is an integer of 1 to 3, m
Is an integer of 6 to 60. )

Examples of the diisocyanate used in the above-mentioned polyether-based urethane (meth) acrylate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate. Examples of the polyether diol include polyoxypropylene glycol, polyoxyethylene glycol, and polyoxytetramethylene glycol having a molecular weight of 500 to 3,000.

Hereinafter, a production example of urethane acrylate will be described. In a glass reaction vessel equipped with a dropping funnel, a thermometer, a reflux condenser, and a stirring rod, 1,000 parts of polytetrameralene glycol having a molecular weight of 1,000 and 444 parts of isophorone diisocyanate were charged and reacted at 120 ° C. for 3 hours. Thereafter, the mixture was cooled to 80 ° C. or lower, 232 parts by weight of 2-hydroxyethyl acrylate was added, and the reaction was carried out at 80 ° C. until the isocyanate group disappeared to obtain a urethane acrylate.

Examples of monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and acrylic acid. Acrylates such as butyl, methoxybutyl acrylate and phenyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate Esters, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl memethacrylate, 2- (N, N-dibenzylamino) methyl acrylate, acrylic Acid-2- (N Substituted amino alcohol esters of unsaturated acids such as N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate ,
Compounds such as 1,6 hexanediol diacrylate and triethylene glycol diacrylate; polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate; and / or Polythiol compounds having two or more thiol groups, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycol.

Usually, one or more of the above compounds may be used as required, or a mixture of two or more of them may be used. In order to impart ordinary coating suitability to the ionizing radiation-curable resin, the prepolymer or polythiol may be used in combination. It is preferable that the content of the monomer and / or polythiol be not more than 95% by weight.

In selecting the monomer, when flexibility of the cured product is required, the amount of the monomer may be reduced as long as the coatability is not impaired, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a relatively low crosslink density. In the case where the abrasion resistance, heat resistance, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder coating suitability, or use a trifunctional or higher acrylate monomer. And a structure having a high crosslinking density can be obtained. In addition, a monofunctional monomer and a trifunctional or higher functional monomer may be mixed to adjust coating aptitude and physical properties of a cured product.

The above-mentioned monofunctional acrylate monomer includes 2-hydroxyacrylate, 2-hexyl acrylate, phenoxyethyl acrylate and the like. Examples of the bifunctional acrylate include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate include trimethylolpropane triacrylate, pentaerythritol tri (tetra) acrylate, and dipentaerythritol hexaacrylate. Acrylate and the like.

Further, a non-ionizing radiation curable resin for adjusting physical properties such as flexibility and surface hardness of the cured product can be added to the ionizing radiation curable resin. As the ionizing radiation non-curable resin, thermoplastic resins such as urethane-based, cellulose-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate are used. Particularly, cellulose-based and urethane-based resins are used. Butyral is preferred from the viewpoint of flexibility.

When irradiating an ultraviolet ray to cure the ionizing radiation-curable resin having the above composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester may be used as a photopolymerization initiator. , Tetramethylthiuram monosulfide,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and photopolymerization accelerators (sensitizers)
N-butylamine, triethylamine, tri-n
-Butylphosphine and the like can be further mixed and used.

The decorative layer 3 may be composed of only the solid print layer 3a or only the pattern print layer 3b. However, when the solid print 3a is provided, the ionizing radiation-curable resin layer 2 is added to the base sheet layer 4. When forming by coating, the solid printing layer 3a can prevent the ionizing radiation-curable resin composition from being excessively impregnated into the base sheet layer 4.

The decorative layer 3 such as the solid printing layer 3a and the picture printing layer 3b may be formed of a known pigment, a coloring agent such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, if necessary. It can be formed by printing with a printing ink obtained by appropriately mixing agents and the like. As the above-mentioned vehicle, a material appropriately selected from thermoplastic resins, thermosetting resins, ionizing radiation-curable resins, and the like according to necessary physical properties, printing suitability, and the like is used.
Further, as the pigment, a commonly used organic or inorganic pigment can be used. As the diluting solvent, a liquid solvent which has a dissolving and dispersing ability for a vehicle resin, a coloring agent such as a pigment, and other additives and has an appropriate drying property is used. Generally, it is preferable from the viewpoint of solubility to select a liquid solvent whose solubility parameter is close to that of the vehicle.

The pattern printing layer 3b is provided in a pattern (for example, a pattern such as wood, cloth, figure, character, etc.) and may be provided on the entire surface of the base sheet layer 2 or may be provided partially. . The pattern printing layer 3b is partially provided, for example, when a part of the pattern (for example, a shining part of a wood pattern) is particularly emphasized. Further, the solid printed layer 7a can be provided, for example, in a case where a solid pearl pattern or an interference appearance is entirely exhibited in a solid pattern.

Although not particularly shown, the base sheet layer 4
A pattern-shaped concave portion may be formed on the surface, and the concave portion may be provided with a wiping ink layer by wiping and filling with a normal coloring ink, or a concave portion and a wiping ink layer may be provided on the surface of the ionizing radiation-curable resin layer 2. The pattern-shaped irregularities can be formed by a known embossing method. The wiping ink layer is formed by applying a coating composition containing a coloring ink on the surface on which the concave portion is formed, and then applying a doctor blade, an air knife, a sponge, or the like on the coated material. Then, the coating composition on the protruding portion is removed with a roller or the like to form a colored ink resin layer only on the recess. In the wiping process, by using a colored coating composition, it is possible to synchronize the pattern and the concave portion with the pattern as a grain, and to reproduce the appearance of the conduit portion of the grain satisfactorily.

The base sheet layer 4 has a basis weight of 20 to 100 g /
m ² of the paper is preferably used. Specifically, thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, sol-coated or dry-laminated polyvinyl chloride resin on paper, so-called vinyl wallpaper raw material, fine paper, coated paper, art paper, Parchment paper, glassine paper, parchment paper,
Examples include paraffin paper and Japanese paper. Further, a paper-like sheet can also be used as the base material. Examples of the above-described paper-like sheet include woven or nonwoven fabrics using inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, polyesters, and organic resins such as vinylon. .

The paper used for the base sheet layer 4 includes:
From the viewpoint of adhesiveness to the inorganic base material, a general paper grade of thin paper is preferred. When laminating the base sheet layer 4 to the inorganic base material via the adhesive resin layer, the general paper grade is easy to adjust the impregnation amount of the adhesive resin, while the impregnated paper grade is insufficient in the impregnation amount of the adhesive resin. In addition, the titanium paper grade tends to have an excessively large amount of impregnation, and the adhesive resin may not remain on the surface.

The adhesive resin layer 5 may be any material that can be impregnated into the base material sheet layer 4 and can be bonded to the inorganic base material layer 6, and is particularly preferably a thermosetting resin. Specifically, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, unsaturated polyester resins, polyurethane resins (including two-pack polyurethanes), epoxy resins, amino alkyd resins, and melamine-urea resins Examples include a condensation resin, a silicon resin, and a polysiloxane resin. The adhesive resin layer 5 is preferably a diallyl phthalate resin from the viewpoint of good heat resistance.

The inorganic base material layer 6 is made of a gypsum-based plate such as a gypsum plate or a gypsum slag plate, a calcium silicate plate, an asbestos slate plate, a lightweight foamed concrete plate, a cement plate such as a hollow extruded cement plate, a pulp cement plate, or an asbestos cement. Board, fiber cement board such as wood chip cement board, pottery, magnetic, stoneware, earthenware,
Ceramic plates such as glass and enamel may be used.

The surface of the plate constituting the inorganic base material layer 6 is preferably subjected to a sealer treatment in order to reinforce the surface of the inorganic plate and seal alkali from the inorganic plate. For the sealer treatment, means for applying a urethane-based or acrylic-based resin by a method such as roll coating or flow coating is used. The surface of the inorganic base material is reinforced by the sealer treatment, so that it is difficult to peel off. In the sealer treatment, since the porous state of the surface of the inorganic base material is maintained, the adhesive resin is impregnated into the inorganic base material and the adhesive strength is good.

FIG. 2 is a process chart for explaining a method of manufacturing the decorative board of FIG. Hereinafter, a method for manufacturing a decorative board will be described with reference to FIG. A base sheet layer 4 such as paper is prepared as shown in FIG. 1A, and a solid print layer 3a and a picture print layer 3b are formed on the surface of the base sheet layer 4 as shown in FIG. The decoration layer 3 is provided by sequentially forming. Next, as shown in FIG. 3C, an ionizing radiation-curable resin composition is applied from above the decorative layer 3 and irradiated with ionizing radiation to form the ionizing radiation-curable resin layer 2 and a decorative sheet. Get 8. An inorganic base material 6 is prepared, and the decorative sheet is laminated on the base material as shown in FIG. I do. The surface of the inorganic base material 6 to be laminated with the decorative sheet is subjected to a sealer treatment to provide a sealer layer 7 in advance.

To laminate the decorative sheet 8 and the inorganic base material layer 2, as shown in FIG. 2D, the opposite side of the decorative sheet base material layer 4 on which the decorative layer 3 is provided, and the inorganic base material layer Material layer 6
To the sealer 7 surface. When the adhesive resin is applied to the base sheet layer 4, when the base sheet layer is paper or the like, a part of the resin is impregnated and partially impregnated into the base sheet layer and cured. Therefore, as compared with a case where a resin that does not penetrate the resin is used as the base sheet layer, peeling is less likely to occur between the base sheet 4 of the decorative sheet 8 and the inorganic base layer 6. Further, when a part of the adhesive resin is impregnated into and impregnated into the inorganic base material layer 6 and cured, a stronger bond can be obtained.

The following means is used for forming the ionizing radiation-curable resin layer 2. A direct coating method in which the coating composition is directly applied to the surface of the substrate 2, a transfer coating method in which the coating composition is previously formed on the surface of the releasable substrate, and then transferred to the surface of the substrate 2 are used. In general, when a material that does not penetrate the coating composition is used as the base sheet, any of the above and any of the above may be used, but paper or the like that penetrates the coating composition was used as the base sheet 2. In the case or a substrate having an uneven surface, and, if the uniformity of the coating thickness is to be obtained, if the intensity of ionizing radiation is to be uniform to form a uniform abrasion resistance, the transfer coating method described above, Although there is an advantage that the problem of resin infiltration does not occur, the number of steps is increased in manufacturing. On the other hand, the direct coating method has a problem of soaking, but since the resin layer can be directly formed on the surface of the base material, the manufacturing is easy if there is no problem of soaking into the base material sheet. There are advantages. From this point, when paper is used as the base sheet, if the solid print layer 3a is formed as the decorative layer 3,
When performing direct coating in which the ionizing radiation-curable resin composition is applied directly to the surface of the base sheet and cured, the solid printed layer 3a impregnates the paper as the base sheet with the ionizing radiation-curable resin. It is possible to form an ionizing radiation-curable resin layer having a uniform thickness and a uniform thickness by effectively preventing it.

The above direct coating method includes gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat , A comma coat, a pouring coat, a brush coat, a spray coat and the like can be used, and a gravure coat is preferable.

When an ionizing radiation irradiator used for curing an ionizing radiation-curable resin is irradiated with ultraviolet light, a light source such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used. Used, and when irradiating with an electron beam,
Various electron beam accelerators such as a Cockloft-Walton type, a Vandegraf type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type and a high frequency type are used.

The irradiation amount of the electron beam is usually 100 to 1000
Electrons having an energy of keV, preferably 100 to 300 keV, are irradiated at a dose of about 0.1 to 30 Mrad. When the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and when the irradiation amount exceeds 30 Mrad, the cured coating film or the base material may be damaged. In addition, the irradiation amount when curing with ultraviolet light is
Preferably it is 50 to 1000 mJ / cm ² . If the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing may be insufficient, and if the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film may turn yellow.

The cosmetic material of the present invention has good abrasion resistance and is suitable for various uses. For example, it can be used for decoration of surfaces of buildings, vehicle ships, furniture, musical instruments, cabinets and the like. In particular, since it has good water resistance, stain resistance and the like, it can be optimally used for wall materials around kitchens and the like.

[0045]

EXAMPLES Example 1 A sheet made of Tenma Special Paper OPA-50 (basis weight: 5) was used as a base sheet.
0 g / m ² ), and solid printing and picture printing were performed on the base sheet by a gravure printing method to provide a picture. HAT manufactured by The Inktec was used as the printing ink. An ionizing radiation-curable resin having the following composition was applied on the pattern to obtain a decorative sheet. Next, diallyl phthalate (DAP) resin dissolved in an organic solvent was applied by roll coating on the surface opposite to the design surface of the decorative sheet (coating amount: 20 g).
/ M ² ). Next, a 4 mm thick calcium silicate plate and DA
Heat press the P resin coated surfaces together (Breath condition:
130-150 ° C, 13-15 kg / cm ² , 7-8 minutes) to obtain a decorative board.

[Ionizing radiation curable resin layer coating composition]-Urethane acrylate oligomer 50 parts by weight-Bifunctional acrylate monomer 40 parts by weight-Trifunctional acrylate monomer 10 parts by weight-Silicone acrylate 3 parts by weight-Spherical alumina (particle size : 25 μm) 20 parts by weight

Comparative Example 1 A decorative plate was obtained in the same manner as in Example 1 except that the ionizing radiation-curable resin layer of Example 1 was not provided.

Reference Example 1 A conventional low-pressure melamine decorative board was used as a reference example.

The decorative boards of Example 1, Comparative Example 1 and Reference Example 1 were tested for abrasion resistance, water resistance and stain resistance.
Table 1 shows the results. As shown in the test results, the decorative board of Example 1 had good properties. The test method is as follows. [Wear resistance] According to JIS K6902 2.9. [Water resistance] According to JAS special plywood water resistance B test. [Stain resistance] JAS special plywood Same as the contamination B test.
As the contaminants, black quick-drying ink and red crayon were used.

[0050]

[Table 1]

[0051]

As described above, the decorative board of the present invention is characterized in that the ionizing radiation-curable resin layer containing spherical alumina having an average particle size of 3 to 50 μm, a decorative layer, a base sheet layer, an adhesive resin layer, an inorganic base By adopting a configuration in which the material layers are sequentially laminated, it is possible to obtain an effect of being excellent in water resistance, stain resistance, wear resistance, and the like, and being easy to manufacture.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of the decorative board of the present invention.

2 (a) to 2 (d) are process diagrams showing an example of a method for manufacturing the decorative board of FIG.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative board 2 Ionizing radiation curable resin layer 3 Decorative layer 4 Base sheet layer 5 Adhesive resin layer 6 Inorganic base layer

Continued on the front page F-term (reference) 2E110 AA12 AA26 AA65 AB03 AB04 AB05 BA04 BA12 BB02 GA05W GA23W GA24X GA32Z GA33X GA42Z GA43W GB12W GB12Z GB16X GB17X GB19X GB19Z GB23X GB26X GB28X GB32X GB32Z GB35Z GB01A GBAZ GB35A AT00C AT00D BA04 BA07 BA10A BA10D CB00 DE01A DG10 GB08 GB81 HB00B JB07 JB13C JB13D JB13G JB14A JK09 JL02 JL06

Claims (3)

[Claims] 1. An ionizing radiation-curable resin layer containing spherical alumina having an average particle size of 3 to 50 μm, a decorative layer, a substrate sheet layer, an adhesive resin layer, and an inorganic substrate layer are sequentially laminated. And decorative board. 2. The decorative board according to claim 1, wherein the base sheet layer and the inorganic base layer are impregnated with an adhesive resin. 3. The method according to claim 1, wherein the adhesive resin is a thermosetting resin.
Or the decorative plate according to 2.