JP2000117909A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in abrasion resistance and design properties and easy to produce. SOLUTION: Decorative treatment comprising printing layers such as a solid printing layer 2, a pattern layer 3 or the like is applied to the surface of a base material sheet 1 and an abrasion-resistant resin layer 4 comprising a crosslinking curable resin containing spherical particles with a particle size of 3-50 μm, a liquid repelling ink layer 5 and a surface protective layer 6 comprising a two-pack type curable urethane resin are successively laminated to the printing layers and the surface protective layer 6 on the liquid repelling ink layer is formed so as to become recessed parts to obtain a decorative sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a decorative sheet.

[0002]

2. Description of the Related Art Conventionally, a decorative sheet formed by printing a pattern or the like on a base sheet such as paper or film, and further laminating an abrasion-resistant resin layer made of a crosslinkable resin containing spherical particles on the surface thereof. It is publicly known (JP-A-8-183147).

[0003]

However, the above decorative sheet is excellent in abrasion resistance, but has insufficient surface design. Further, the above publication describes that a pattern-shaped concave portion is formed, and a wiping ink layer is provided in the concave portion to form a colored pattern. However, the above-mentioned wiping involves steps such as ink filling, scraping work, and curing of the ink, and has a problem that the work is complicated. Further, since the formed ink layer is exposed on the surface, there is a drawback that durability is inferior.

The present invention has been made to solve the above-mentioned drawbacks of the prior art, and an object of the present invention is to provide a decorative sheet which is excellent in abrasion resistance, excellent in design, and easy to manufacture.

[0005]

According to the present invention, there is provided (1) a method in which a particle size of 3 to 50 μm
A decorative sheet, characterized in that an abrasion-resistant resin layer made of a cross-linking curable resin containing spherical particles of a, a liquid-repellent ink layer, and a surface protective layer made of a two-liquid curable urethane resin are sequentially laminated, Is the gist.

[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 sheet of the present invention is subjected to a decoration process including a printing layer such as a solid printing layer 2 and a pattern printing layer 3 on the surface of a base sheet 1, and spherical particles having a particle size of 3 to 50 μm are formed. The abrasion-resistant resin layer 4 made of the cross-linking-curable resin contained therein, the liquid-repellent ink layer 5, and the surface protective layer 6 made of the two-component curable urethane resin are sequentially laminated, and the liquid repellent of the surface protective layer 6 is formed. The upper part of the conductive ink layer is formed as a concave portion 7.

As the substrate sheet 1, paper, plastic, metal foil, plate, or the like is used, but a flexible sheet is used. In the manufacturing process, a roll of the sheet is used as a substrate. This is preferable because continuous production of decorative sheets is possible. Normally, when a sheet-like substrate sheet 1 is used, a sheet having a thickness of 5 to 200 μm is preferably used. Further, as the base sheet 1, a sheet having irregularities on its surface, a sheet having a three-dimensional shape, or the like can be used.

[0008] The paper used for the base sheet 1 is specifically a so-called vinyl wallpaper obtained by sol-coating or dry-laminating a polyvinyl chloride resin on paper, such as tissue paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper. Raw paper, high-quality paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like. Further, a paper-like sheet can also be used as the base sheet. 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. . Further, impregnated paper obtained by impregnating a resin with the above-mentioned paper or paper-like sheet as a base paper can also be used. The base paper of the impregnated paper has a basis weight of 20 to 1
20 g / m ² is preferable, and titanium paper mixed with a concealing pigment such as titanium oxide is particularly preferable because the concealing property of the lower layer is excellent when the decorative sheet is attached to another substrate.

The plastic sheet used as the base sheet 1 includes polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, ethylene-acetic acid. Vinyl resins such as vinyl copolymers, ethylene-vinyl alcohol copolymers, and vinylon; polyester resins such as polyethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate-isophthalate copolymers; polymethyl methacrylate, polymethacrylic Acrylic resins such as ethyl acrylate, polyethyl acrylate, and polybutyl acrylate; polyamides such as nylon 6 and nylon 66;
Cellulose resins such as cellulose triacetate and cellophane,
Monolayer or laminate of a synthetic resin film such as polystyrene, polycarbonate, polyarylate, polyimide or the like, or sheet. Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The base sheet 1 may be a composite base material obtained by laminating two or more of the above various base materials by a known means such as an adhesive or heat fusion.

The solid printing layer 2 used in the decoration process may be either full-area solid printing or partial solid printing. The pattern print layer 3 is made of a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, a picture, or a pattern of various abstract patterns. These print layers may be composed of only the pattern print layer 3, only the solid print layer 2, or both of the pattern print layer 3 and the solid print layer 2.

The printing layers 2 and 3 can be formed by printing or coating using a general printing ink. The ink includes a binder and a colorant. Examples of the binder include chlorinated polyethylene, chlorinated polyolefins such as chlorinated polypropylene, polyester, polyurethane (two-component curable urethane resin or thermoplastic urethane resin), acrylic, One or a mixture of two or more of polyvinyl acetate, a vinyl chloride / vinyl acetate copolymer, a cellulose resin, and the like is used. Examples of the coloring agent include pigments or dyes such as titanium white, carbon black, red iron oxide, graphite, ultramarine, phthalocyanine blue, quinacridone, and isoindolinone; metal foil powders such as aluminum and brass; and foils such as titanium dioxide-coated mica. One type or a mixture of two or more types of powdery light-emitting pigments may be used.

The printing layers 2 and 3 can be printed by a known method similar to ordinary printing, such as gravure printing, offset printing, letterpress printing, screen printing, and the like. In addition, as a method of applying the print layer, known coating means such as a gravure coat, a roll coat, and a flow coat can be used.

The wear-resistant resin layer 4 is formed from a coating composition containing at least a cross-linkable curable resin as a binder and spherical particles. The spherical particles are added to impart abrasion resistance to the abrasion resistant resin layer 4. As the cross-linking curable resin, an ionizing radiation curable resin or a thermosetting resin is used. The wear-resistant resin layer is formed by applying the above-mentioned coating composition from above the picture layer 3 and curing it. The thickness of the wear-resistant resin layer 4 is preferably 5 to 100 μm.

The spherical particles need only be surrounded by a smooth curved surface, such as a true sphere, an elliptical sphere obtained by flattening a sphere, and a shape close to the true sphere or ellipsoid. The spherical particles preferably have no protrusions or corners on the particle surface, and have no so-called cutting edge. Spherical particles greatly improve the abrasion resistance of the resin layer itself as compared to amorphous particles of the same material, and do not wear the coating device, and remove other objects that come into contact with this even after the coating is cured. Without abrasion,
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.

The coating composition is preferably adjusted so that the amount of spherical particles contained in the wear-resistant resin layer 4 is 5 to 20 parts by weight based on 100 parts by weight of the resin component. When the addition amount of the spherical particles is small, there is a possibility that the effect of the addition of the spherical particles such as improvement of the abrasion resistance may not be sufficiently exerted. On the other hand, when the addition amount of the spherical particles is too large, the effect as the binder of the resin may be insufficient. Damage may be caused, and the flexibility of the coating film may be reduced, and the workability of the coating composition may be reduced.

As the material of the spherical particles, any of inorganic particles and organic resin particles can be used, but it is preferable that the difference in hardness from the crosslinkable resin is, for example, 1 or more when expressed in Mohs hardness. The spherical particles preferably have a Knoop hardness of 1300 kg / mm ² or more, and more preferably a Knoop hardness of 1800 kg / mm ² or more.
In addition, the Knoop hardness referred to here is a small indentation type measured using a Knoop indenter, and the load when a diamond-shaped indentation was applied before the test was obtained from the length of the longer diagonal line of the permanent dent. It is a value represented by a quotient divided by the projected area of the dent. This test method is described in ASTM C-849.

Specific examples of the material of the spherical particles include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond, and graphite, and organic resin particles such as synthetic resin beads such as cross-linked acryl. Can be Examples of the above-mentioned α-alumina include fused alumina, Bayer alumina, and the like, and other inorganic particles include zirconia, titania, or a eutectic mixture of these, fused alumina, and Bayer alumina. As a method of making the shape of these inorganic particles spherical, a method in which the above-mentioned crushed amorphous inorganic compound is charged into a high-temperature furnace having a melting point or higher and melted, and a method of making the inorganic material spherical by using surface tension, or the above-mentioned inorganic material is used. A method in which a material melted at a high temperature equal to or higher than the melting point is blown out into a mist and formed into a sphere is exemplified.

Particularly preferred spherical particles include spherical α-alumina because they have very high hardness and a large effect on abrasion resistance, and spherical particles are relatively easily obtained. As described in JP-A-2-55269, spherical α-alumina is obtained by adding a mineralizing agent or a crystallizing agent such as alumina hydrate, a halogen compound or a boron compound to a fused alumina or a sintered alumina. By adding a small amount to the pulverized product and subjecting it to a heat treatment at a temperature of 1400 ° C. or more for 2 hours or more, a cutting edge in alumina is reduced and, at the same time, a spherical shape can be obtained. Such a spherical alumina is available from Showa Denko KK as "Spherical Alumina AS".
-10, AS-20, AS-30, AS-40, AS-
Various average particle sizes of 50 "are commercially available.

The spherical particles can be treated on their 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 binder resin and the dispersibility of the particles in the coating composition are improved. As the silane coupling agent, alkoxysilane having a radical polymerizable unsaturated bond such as vinyl or methacrylic in the molecule,
An alkoxysilane having a functional group such as epoxy, amino, and mercapto in a molecule is exemplified. The silane coupling agent may be, for example, an alkoxysilane having a radical polymerizable unsaturated bond in the case of an ionizing radiation curable resin using (meth) acrylate or the like, depending on the type of the crosslinkable curable resin used together with the spherical particles. In the case of a two-part curable urethane resin, it is preferable to select the type of radically polymerizable unsaturated bond or functional group, such as using an alkoxysilane having an epoxy group or an amino group. The alkoxysilane having a radical polymerizable unsaturated bond is specifically, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropyldimethylmethoxysilane,
γ-methacryloxypropyldimethylethoxysilane,
γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxy There are alkoxysilane having a radical polymerizable unsaturated bond in a molecule such as propyldimethylethoxysilane and vinyltriethoxysilane, and alkoxysilane having a functional group such as epoxy, amino and mercapto in a molecule.

A known method can be used for treating the surface of the spherical particles with a silane coupling agent. For example, a method in which a predetermined amount of a silane coupling agent is sprayed while vigorously stirring the spherical particles (dry method). After the spherical particles are dispersed in a solvent such as toluene, a predetermined amount of the silane coupling agent is added and reacted. Method (wet method). The processing amount (required amount) of the silane coupling agent for the spherical particles 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 the spherical particles of 100. When the minimum covering area of the spherical particles is less than 10 with respect to the specific surface area of the spherical particles of 100, the effect is not so large.

Spherical particles having a particle diameter of 3 to 50 μm (average particle diameter) are used. The average particle size of the spherical particles is 3 μm
If less than 50 μm, the film becomes opaque, and if it exceeds 50 μm, the surface smoothness of the film decreases. As the particle size of the spherical particles decreases, the abrasion resistance decreases. On the other hand, when the particle diameter of the spherical particles is large, the abrasion resistance is improved. However, when the particle diameter is too large, uniform coating at the time of coating becomes difficult.

The ionizing radiation-curable resin constituting the wear-resistant resin layer 4 is, specifically, a prepolymer or oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule.
And / or a composition which is appropriately mixed with a monomer and which can be cured by ionizing radiation is used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking 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 -CONH-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 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 the 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 are used as needed, and a mixture of the above prepolymer or polythiol is used in order to impart ordinary coating suitability to the ionizing radiation-curable resin. It is preferable that the content of the monomer and / or polythiol be not more than 95% by weight.

When irradiating ultraviolet rays to cure the ionizing radiation-curable resin, acetophenones, benzophenones, Michler benzoyl benzoate, α-amino oxime ester, tetramethylthiuram monosulfide, Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and n-butylamine, triethylamine, tri-n-butylphosphine, and the like as a photopolymerization accelerator (sensitizer) can be further mixed and used. .

When an ionizing radiation irradiator used for curing an ionizing radiation-curable resin is irradiated with ultraviolet light, a light source such as an ultra-high 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 thermosetting resin used for the wear-resistant resin layer 4 includes phenol resin, urea resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin (Including two-pack type polyurethane), epoxy resin, amino alkyd resin, melamine-urea co-condensation resin, silicon resin, polysiloxane resin and the like. If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, etc. may be added and used. As the above curing agent, isocyanates or organic sulfonates are usually used in unsaturated polyester resins or polyurethane resins, amines are used in epoxy resins, peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutyl nitrile are used. Often used for saturated polyesters.

As the above-mentioned isocyanate, divalent or higher valent aliphatic or aromatic isocyanate can be used, but aliphatic isocyanate is preferable from the viewpoint of prevention of thermal discoloration and weather resistance. Specific isocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

As the two-pack type polyurethane, a first solution consisting of a polyol compound having an average of two or more hydroxyl groups in its molecular structure and a second solution consisting of a polyisocyanate compound are prepared by combining a hydroxyl group and an isocyanate group. What was blended so that equivalent ratio might be set to 0.7-1.5 is mentioned.

The epoxy resin includes an epoxy resin having an average of two or more epoxy groups in its molecular structure and a mono- or poly-amine having three or more active hydrogens in one molecule which react with the epoxy group. Examples include those blended such that the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the mono or polyamine is 0.7 to 1.5.

The composition of the abrasion-resistant resin layer 4 includes, as components other than the binder resin and the spherical particles, coloring agents such as dyes and pigments, and other known matting agents such as CaCO ₃ , BaSO ₄ and nylon resin beads. Additives that are usually added to paints and inks, such as fillers such as adjusters and extenders, defoamers, leveling agents, and thixotropic agents can be added.

In order to adjust the viscosity, the composition of the abrasion-resistant resin layer 4 is capable of dissolving a resin component, and contains a solvent having a boiling point of 70 ° C. to 150 ° C. at normal pressure in the composition. Can be used in a range of 30% by weight or less. When the amount of the solvent added is in the range of 30% by weight or less, drying is smooth, and there is no significant decrease in production speed.

As the above-mentioned solvent, those which are usually used for paints, inks and the like can be used. Specific examples thereof include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Acetates such as ethyl acetate, isopropyl acetate, and amyl acetate; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ethers such as dioxane, tetrahydrofuran, and diisopropyl ether; and mixtures of two or more of these. .

In order to impart flame retardancy to the decorative sheet, a powder of a flame retardant such as aluminum hydroxide or magnesium hydroxide may be added to the base sheet 1 or the wear-resistant resin layer 4 or the like. Further, in order to impart antibacterial properties to the decorative sheet, an antibacterial agent such as zeolite powder carrying silver ions or a 10,10′-oxybisphenoxyarsine or the like is added to the base sheet 1 or the wear-resistant resin layer 4 or the like. A fungicide or the like may be added.

The method for forming the abrasion-resistant resin layer 4 is a direct coating method of directly applying a coating composition, or
After forming a wear-resistant resin layer on the peelable substrate surface in advance,
A transfer coating method of transferring the layer to the surface of the substrate 2 is used.

The above direct coating methods include 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.

The transfer coating method is a method in which a coating is formed on a thin sheet (film) substrate as shown in the following (a) to (d), cross-linked and cured, and then coated on the surface of the substrate. A laminating method (a, b) in which a coating film of a coating composition is adhered to a three-dimensional object together with a substrate, and a coating film and, if necessary, an adhesive layer are formed on a release support sheet to form a coating film. A transfer method (c) or the like in which the transfer sheet formed by crosslinking and curing is bonded to the three-dimensional object on the coating film side and then the support sheet is peeled off only can be used. In addition, on a thin sheet substrate,
As the method for forming the wear-resistant resin layer, the same various coating means as used in the direct coating method described above can be used. (A) JP-B-2-42080, JP-B-4-199
No. 24, etc., simultaneous injection molding transfer method.
Alternatively, an injection molding simultaneous lamination method as disclosed in Japanese Patent Publication No. 50-19132. (B) JP-A-4-288214, JP-A-5-57
No. 786, a vacuum forming simultaneous transfer method.
Alternatively, a vacuum forming simultaneous lamination method as disclosed in JP-B-56-45768. (C) JP-B-59-51900, JP-B-61-5
No. 895, JP-B-3-2666, etc., a lapping simultaneous transfer method or a lapping simultaneous lamination method. (D) V-cut simultaneous lamination method disclosed in Japanese Utility Model Publication No. 15-31122 or Japanese Patent Publication No. 56-31122.
V-cut simultaneous transfer method disclosed in JP 7866 and the like.

As one of the transfer coating methods described above, for example, when an ionizing radiation-curable resin is used as the crosslinkable resin, a method in which the following steps (A) to (D) are sequentially performed may be used. (Described in JP-A-2-26673). (A) A step of applying an uncured liquid ionizing radiation-curable resin composition to a non-absorbable and releasable synthetic resin sheet. (B) a step of laminating so that the application surface of the ionizing radiation-curable resin composition is in contact with a substrate. (C) a step of irradiating the coating film of the ionizing radiation-curable resin composition with ionizing radiation to crosslink and cure. (D) a step of peeling and removing the synthetic resin sheet. In the above step, when a resin diluted with a solvent is used as the ionizing radiation-curable resin, a step of drying the solvent is performed between steps (A) and (B).

The lyophobic ink layer 5 is formed by adding a lyophobic substance to the ink composition described in the print layers 2 and 3 and then dispersing and kneading the ink composition using a known printing means. It is formed by printing on the surface of the conductive resin layer 4. As the print pattern, a pattern of a portion to be formed as a concave portion in the surface protective layer 6 is used, and examples thereof include designs such as a wood grain conduit pattern and tile joints.

The liquid-repellent substance may be any substance having the property of repelling ink on the surface protective layer 6, and specific examples of the liquid-repellent substance are described in JP-B-52-2641. Silicone, wax, vinyl fluoride compound and the like are mentioned. As the above silicone,
For example, methyl, propyl, phenyl,
A low molecular weight or high molecular weight linear, side chain, or cyclic structure to which groups such as a halogen atom, an alkoxy, a hydroxyl group, an acetoxyl group, and a metal salt are arbitrarily bonded can be used. Examples of the wax include paraffin wax, amide wax, wax and the like.

In the composition of the liquid-repellent ink, in addition to the above-mentioned liquid-repellent substance, a curing for suppressing the curing of the resin constituting the surface protective layer 7 as described in JP-A-61-2910075. Inhibitors can be added. Specifically, 2
Examples of the substance that suppresses the curing of the liquid-curable urethane resin include a metal chelate compound, an organic acid, and an acrylate having a carboxyl group. When these curing inhibitors are added, the effect of repelling the surface protective layer is stabilized, and the sharpness of the concave portions is further improved.

The surface protective layer 6 is formed by applying and curing a two-component curable urethane resin composition after providing the lyophobic ink layer. The composition of the two-part curable urethane resin is prepared by adding a plasticizer, a stabilizer, a filler, and a dispersion to a vehicle component composed of a polyol component such as polyester polyol, polyether polyol, and acrylic polyol, and an isocyanate component, if necessary. It is obtained by adding a colorant such as an agent, a dye and a pigment, a solvent and the like, and mixing. The surface protective layer 6 is usually formed so as to be transparent enough to see a design such as a lower printed layer. As the components such as the polyol and the isocyanate, those exemplified in the description of the wear-resistant resin layer can be used. A particularly preferred two-part curable urethane resin composition is a combination of an acrylic polyol and a curing agent HDI.

The coating composition for the surface protective layer 6 can be applied using a known coating means such as a gravure coat, a roll coat, and a flow coat. The coating amount of the surface protective layer 6 is preferably from 3.0 to 15.0 g / m ² .

In the decorative sheet of the present invention, the surface protective layer 6
When the coating composition is applied, the coating composition is repelled by the liquid-repellent substance of the liquid-repellent ink layer 5, and the portion is recessed 7.
Is formed as Further, when the curing inhibitor is contained in the liquid repellent ink layer 5, curing of the coating composition of the surface protective layer on the liquid repellent ink layer is suppressed, and the surface protective layer in the portion is not cured. The coating composition moves toward a portion having no curing inhibitor and no liquid-repellent ink layer, and the unevenness appears more clearly in combination with the liquid-repellent action of the liquid-repellent substance.

The surface protective layer 6 may be formed by liquid repelling so that a thin layer is formed above the liquid repellent ink layer as shown in FIG. The liquid may be completely repelled so that there is no surface protective layer above the layer. From the point of protecting the design of the lyophobic ink layer,
As shown in FIG. 1, it is preferable that the surface protective layer is formed so as to slightly cover the upper part of the liquid-repellent ink layer.

When the composition of the surface protective layer 6 made of a two-component curable urethane resin is applied to the surface of the liquid-repellent ink layer 5, the composition is not repelled above the liquid-repellent ink layer. The curing rate is adjusted so that the liquid is sufficiently repellent without being cured before being cured. The adjustment of the curing speed can be adjusted by the boiling point of the solvent used, the amount of the catalyst added, the type, and the like.

The decorative sheet of the present invention can be used as a decorative plate or the like by attaching it to a plate or the like. As the above plate material,
Wood veneer, wood plywood, particle board, wood board such as MDF (medium density fiber board), gypsum board, gypsum board such as gypsum slag board, calcium silicate board, asbestos slate board, lightweight foam concrete board, hollow extruded cement board Cement board, pulp cement board, asbestos cement board, fiber cement board such as wood chip cement board, etc., ceramics board such as pottery, magnetism, stoneware, earthenware, glass, enamel, iron plate, galvanized steel plate, polyvinyl chloride sol coating Steel plate, aluminum plate, metal plate such as copper plate, polyolefin resin plate, acrylic resin plate, ABS
Thermosetting resin plate such as a thermoplastic resin plate such as a plate, a polycarbonate plate, a phenol resin plate, a urea resin plate, an unsaturated polyester resin plate, a polyurethane resin plate, an epoxy resin plate, a melamine resin plate, a phenol resin, a urea resin, Unsaturated polyester resin, polyurethane resin, epoxy resin,
A resin plate such as a so-called FRP plate or the like obtained by impregnating and curing a resin such as a melamine resin or a diallyl phthalate resin into a glass fiber nonwoven fabric, a cloth, paper, or other various fibrous base materials to form a composite.

These decorative sheets or decorative plates can be used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings, floors, window frames, doors, surface makeup of fittings such as handrails,
Examples of such applications include furniture such as wardrobes, surface decoration of cabinets for light electric / OA equipment such as television receivers, vehicle interiors such as automobiles and trains, aircraft interiors, and window glass makeup. In particular, it can be optimally used for applications requiring wear resistance.

[0055]

EXAMPLES Example 1 Solid printing layer using acrylic nitrified cotton-based ink (HAT ink: The Inteck) on the surface of impregnated paper (GF601: manufactured by Kojin) having a basis weight of 60 g / m ² , System ink (M
A pattern printing layer using AX ink (manufactured by The Inktec Co., Ltd.) was formed by printing, and an ionizing radiation-curable resin composition having the following composition was applied by roll coating (coating amount: 25.0 g /
m ² ) and irradiate with an electron beam (175 kv, 5 Mrad)
A wear-resistant resin layer was provided. Furthermore, after providing a liquid-repellent ink layer on the surface of the wear-resistant resin layer by gravure printing using a liquid-repellent ink having the following composition, a two-component curable urethane resin having the following composition is applied by gravure printing (coating). 5 g / m ² )
To form a surface protective layer to obtain a decorative sheet.

[Ionizing radiation-curable resin composition] 50 parts by weight of urethane acrylate oligomer 40 parts by weight of bifunctional acrylate monomer 10 parts by weight of trifunctional acrylate monomer 20 parts by weight of spherical alumina (average particle size 25 μm)

[Liquid-repellent ink composition] Polyol 20 parts by weight Silica extender pigment 20 parts by weight Solvent 60 parts by weight Isocyanate 20 parts by weight Silicone 3 parts by weight Colored pigment

[Two-component curable urethane resin composition]-20 parts by weight of acrylic polyol-5 parts by weight of HDI-3 parts by weight of extender-6 parts by weight of matting agent-60 parts by weight of solvent

[0059]

As described above, the decorative sheet of the present invention has a particle size of 3 on the surface of the decorative base material sheet.
By adopting a configuration in which an abrasion-resistant resin layer made of a cross-linking curable resin containing spherical particles of about 50 μm, a lyophobic ink layer, and a surface protective layer made of a two-liquid curable urethane resin are sequentially laminated. Thus, a decorative sheet having excellent abrasion resistance and excellent design can be obtained. In particular, since the portion corresponding to the pattern of the ink layer is formed as a concave portion by providing the lyophobic ink layer, a design in which the concave portion and the pattern exactly match is obtained, and embossing or the like is performed on the surface protective layer. As a result, a good design can be obtained as compared with the case where the concave portion is provided. Further, as compared with a decorative sheet provided with a concave portion by embossing and provided with a wiping ink layer, steps such as an ink scraping operation and ink curing are unnecessary, and the workability is excellent and the production is easy.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one example of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Solid printing layer 3 Pattern printing layer 4 Abrasion-resistant resin layer 5 Liquid-repellent ink layer 6 Surface protection layer 7 Depression

Continued on the front page F term (reference) 4F100 AA19B AA20C AJ06B AK01B AK25B AK25D AK51B AK51D AK54C AT00A BA04 BA07 BA10A BA10D CA13C CA13D CC00B CC00C DE01B DG10A EJ53B GB08 HB31B JB12B JB12B JB12B JB12B

Claims (1)

[Claims] 1. A wear-resistant resin layer, a liquid-repellent ink layer made of a cross-linking-curable resin containing spherical particles having a particle diameter of 3 to 50 μm, and a surface of a substrate sheet subjected to a decoration treatment.
A decorative sheet, characterized in that a surface protective layer made of a two-component curable urethane resin is sequentially laminated.