JP4491313B2 - Method for painting decorative surface and decorative laminate - Google Patents

Description

  The present invention relates to a method for painting a decorative surface on the surface of a building or a civil engineering structure, and a decorative laminate.

  Conventionally, various decorative coating materials have been painted on the surface of buildings, civil engineering structures, and the like in order to enhance the aesthetics. As such a decorative coating material, a stone finish coating material in which a synthetic resin emulsion is blended with a pulverized natural stone, a colored aggregate, or the like, or two or more color particles in liquid or gel form are suspended in a dispersion medium. Various types of paints, thin finish coating materials and thick finish coating materials defined in JIS A6909 are known. Among these, examples of the stone finish finishing coating material include the coating materials described in Patent Document 1 (Japanese Patent Publication No. 2-40702). Moreover, as a colorful pattern coating material, the coating material etc. which were disclosed by patent document 2 (Japanese Patent Publication No. 1-19705) are mentioned, for example. In the coating of such decorative coating materials, a finishing method is generally adopted in which a clear coating is applied after the decorative coating material is applied in order to ensure coating properties such as contamination resistance and weather resistance. ing.

  Specifically, Patent Document 3 (Japanese Patent Laid-Open No. 57-27177) discloses a decorative wall finishing method expressing a natural stone pattern, such as acrylic resin emulsion and marble powder, granite powder, colored cinnabar sand, colored ceramic powder, and the like. After applying the spray material made by mixing the materials to form a concavo-convex pattern, the top of the convex part is cut flat after drying, and then the entire surface is coated with a transparent acrylic resin or transparent acrylic-urethane resin. The method of finishing is described.

  Patent Document 4 (Japanese Patent Laid-Open No. 5-177164) relates to a method for constructing a natural stone-like, polished stone-like finish surface, and a coating material composed of an emulsion resin, natural stone, and colored aggregate is applied to the gazette. In addition, a method is described in which a coated surface is flattened using a film sheet, plastering iron, or the like, and then a synthetic resin clear paint is applied to finish.

  Patent Document 5 (Japanese Patent Laid-Open No. 8-257490) relates to a natural stone finishing method. This publication describes a method in which a multicolor pattern paint made of an acrylic resin emulsion, a plurality of colored dispersed particles and mica is applied, and then a clear paint made of an acrylic resin or the like is applied to the surface.

  Patent Document 6 (Japanese Patent Laid-Open No. 2000-135471) applies a coating material containing a synthetic resin emulsion and aggregates and / or pigments, and further a coating material containing a synthetic resin emulsion, aggregates and mica flakes It is described that a decorative surface is formed by coating and then a clear paint made of a synthetic resin emulsion or the like is applied to the decorative surface in order to impart performance such as weather resistance and antifouling property.

  In the coating methods described in Patent Documents 3 to 6, the clear coating is a process necessary for improving the physical properties of the coating film such as contamination resistance. However, all of the clear paints described in the above-mentioned patent documents are obtained by using ordinary resins as they are or diluted, and may not provide a sufficient anti-contamination effect in an environment in which contamination tends to proceed. .

  On the other hand, Patent Document 7 (Japanese Patent Laid-Open No. 9-57186) discloses a multi-pattern paint finishing method in which a multi-color paint containing enamel dispersed particles of a plurality of colors is applied and then a clear paint is applied thereon. From the viewpoint of stain resistance, it is described that a clear coating material in which an organosilicate compound is blended with an acrylic resin, urethane resin, silicon resin, or fluororesin resin is described. In the clear coating, it can be expected that the organosilicate compound acts as a low contamination agent.

  However, the organosilicate compound used in the clear coating described in Patent Document 7 has an alkoxysilyl group having reactivity with water. Therefore, when an organosilicate compound is added to a clear coating, the hydrolysis condensation reaction cannot be controlled, the viscosity of the coating suddenly increases in a short time, and the entire coating is gelled. May cause trouble. In addition, the compatibility between the resin and the silicate compound is poor, and there is a problem that aggregates are formed after mixing and the sharpness of the coating film is impaired. Furthermore, even when coating is performed immediately after mixing and a coating film is formed, there is a drawback that sufficient stain resistance cannot be obtained. In particular, in the initial stage of coating film formation, there is a problem that contaminants easily adhere due to the adhesiveness caused by the organosilicate compound or the like.

Japanese Patent Publication No. 2-40702 Japanese Patent Publication No. 1-19705 JP-A-57-27177 JP-A-5-177164 JP-A-8-257490 JP 2000-135471 A JP-A-9-57186

  The present invention has been made in view of the above-mentioned problems in the coating of decorative coating materials, and the object of the present invention is excellent in sharpness, stain resistance, etc. without causing any trouble in the painting operation. It is to obtain a paint finishing method capable of forming a coated film.

  As a result of intensive studies in order to solve these problems, the present inventor has applied a method for applying a water-based clear paint having a specific synthetic resin emulsion and neutral silica sol as essential components after coating a decorative coating material. As a result, the present invention has been completed.

That is, the present invention has the following features.
1. After applying a decorative coating material to the base material to form a multicolor pattern or uneven pattern,
Essential components are a synthetic resin emulsion (A) having a pH of 4.0 to 10.0 and a neutral silica sol (B) having a particle diameter of 1 to 200 nm and a pH of 5.0 to less than 8.5. And, based on 100 parts by weight of the solid content of the synthetic resin emulsion (A), an aqueous clear paint containing 0.1 to 50 parts by weight of the neutral silica sol (B) in terms of solid content is applied. How to finish the decorative surface.
2. The neutral silica sol is hydrophobized. The coating finish method of the decorative surface as described in 1.
3. A decorative laminate having a base material layer, a decorative layer, and a clear layer,
The decorative layer has a multicolor pattern or an uneven pattern,
The clear layer has a synthetic resin emulsion (A) having a pH of 4.0 to 10.0, and a neutral silica sol having a particle diameter of 1 to 200 nm and a pH of 5.0 to less than 8.5 ( B) is an essential component, and is formed of an aqueous clear paint containing 0.1 to 50 parts by weight of the neutral silica sol (B) in terms of solids with respect to 100 parts by weight of the solids of the synthetic resin emulsion (A). A decorative laminate characterized in that the decorative laminate.
4). 2. The neutral silica sol is hydrophobized. The decorative laminate as described in 1.

In the water-based clear paint used in the present invention, the increase in paint viscosity is suppressed, the handling in the painting work is easy, and the efficiency of the painting work can be increased.
Furthermore, the decorative surface formed by the paint finishing method of the present invention has excellent sharpness and exhibits excellent stain resistance. In particular, it has a feature that contaminants hardly adhere even at the initial stage of coating film formation.

  Hereinafter, the best mode for carrying out the present invention will be described.

I. Coating Finishing Method First, of the embodiments of the present invention, a method for coating a base material with a decorative coating material and a water-based clear coating in order will be described below.

[1] Substrate The present invention can be used mainly for surface finishing of buildings and civil engineering structures. Applicable base materials include, for example, concrete, mortar, porcelain tile, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement board, ALC board, siding board, extrusion board, steel sheet, plastic board , Gypsum board, plywood and the like. The surface of these base materials can be coated after some surface treatment (for example, sealer, surfacer, filler, putty, etc.) is applied.

[2] Decorative coating material In the present invention, a multicolor pattern or an uneven pattern is formed by applying a decorative coating material to the substrate. Any decorative coating material can be used without particular limitation as long as it can form a multicolor pattern or an uneven pattern. The multicolor pattern referred to here is a pattern in which at least two or more colors are mixed in a visible state. The uneven pattern is a surface pattern having a height difference of about 0.2 to 5 mm.

  Specific examples of the decorative coating material include (1) stone finish finishing coating material, (2) JIS K5667 colorful pattern coating material, and (3) JIS A6909 thin finishing coating material / thickening finishing coating material. .

[Stone finish coating material]
The stone finish finishing coating material is a coating material capable of forming a multicolor pattern by coloring the aggregate, and is a coating material having a synthetic resin emulsion and an aggregate as essential components. Among these, examples of the synthetic resin emulsion include vinyl acetate resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic urethane resin, acrylic silicon resin, fluororesin, and a composite system thereof.

As the aggregate, an aggregate having a particle diameter of 0.05 to 5 mm is usually used. As such an aggregate, at least one selected from natural aggregates such as natural stone and natural stone pulverized products, and artificial aggregates such as colored aggregates can be suitably used. Specifically, for example, marble, granite, serpentine, granite, fluorite, cryolite, feldspar, limestone, quartzite, quartz sand, crushed stone, mica, siliceous shale, and pulverized products thereof, ceramic pulverized products, ceramic pulverized products Products, crushed glass, glass beads, crushed resin, resin beads, rubber particles, metal particles, and the like. In addition, pulverized products such as shells, shells, wood, charcoal, activated carbon and the like can be used. Furthermore, those whose surfaces are colored and coated by performing surface treatment with pigments, dyes, glazes, and the like can also be used. By using two or more kinds of such aggregates in appropriate combination, various multicolor patterns can be expressed.
The aggregate is usually mixed at a ratio of 100 to 4000 parts by weight, preferably 150 to 3000 parts by weight, more preferably 200 to 2000 parts by weight with respect to 100 parts by weight of the solid content of the synthetic resin emulsion. If the mixing ratio of the aggregate is within such a range, it is preferable in terms of the design properties of the formed coating film, crack prevention properties, and the like.

  Components other than those described above can be mixed in the stone finish finishing coating material. Examples of such components include coloring pigments, extender pigments, fibers, film-forming aids, plasticizers, antifreezing agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, pigment dispersants, thickeners. , Leveling agents, wetting agents, pH adjusting agents, matting agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents and the like.

As a method for applying the stone finish finishing coating material, for example, spray coating, roller coating, trowel coating, brush coating, and the like are possible, and one or more coating materials may be applied in layers. In such a stone finish finishing coating material, various uneven patterns can be imparted by appropriately selecting and adjusting a painting tool, coating conditions, and the like. Moreover, it is also possible to cut a convex part with a sander etc. after coating film drying. Tile patterns, geometric patterns, etc. can be formed by using joint rods or joint molds.
The coating amount of the stone finish finishing coating material is usually about 1 to 10 kg / m ² . At the time of application, a diluent such as water can be mixed to appropriately adjust the viscosity of the coating material. The dilution ratio is usually about 0 to 10% by weight. The stone finish finishing coating material may be usually dried at room temperature.

[Multicolored paint]
The multicolor paint is a liquid or gel-like color particle having two or more colors suspended in a dispersion medium. These are (1) oil-in-water type (O / W type), (2) water-in-oil type (W / O type), (3) oil-in-oil type (O / O type), (4) water-in-water type (W / W type). Among these, the oil-in-water type (O / W type) and the water-in-water type (W / W type) multicolored paints are both preferable in terms of environment and the like because the dispersion medium is aqueous.

The color particles in the multicolored paint are obtained by dispersing a colored paint containing a resin, a colorant, and various additives as required in a dispersion medium.
The resin in the colored paint is not particularly limited as long as it functions as a vehicle for the paint. Examples of such a resin include acrylic, urethane, vinyl acetate, vinyl acrylate, acrylic urethane, acrylic silicon, fluorine, polyvinyl alcohol, biogum, galactomannan derivatives, alginic acid derivatives, and cellulose derivatives. The form of these resins may be any of a solvent-soluble resin, a non-aqueous dispersion resin, a water-soluble resin, a water-dispersible resin, and the like. These resins may have a functional group that can be cross-linked by a curing agent or a curing catalyst.

  When the resin is a solvent-soluble resin and / or a non-water-dispersible resin, a solvent-type colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, an oil-in-water type (O / W type) is obtained. It becomes a multicolored paint. Further, when the resin is a water-soluble resin and / or a water-dispersible resin, an aqueous colored paint is obtained. When this resin is dispersed in an aqueous dispersion medium, a water-in-water type (W / W type) multicolor pattern paint and Become.

  As the colorant in the colored paint, those that can be generally added to the paint can be used. Specifically, for example, titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, brown, molybdate orange, permanent red, permanent Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine A violet, an aluminum pigment, a pearl pigment, etc. are mentioned, These 1 type (s) or 2 or more types can be used.

  In the colored paint, known paint additives can be appropriately used. Such additives include, for example, viscosity modifiers, crosslinkers, catalysts, fillers, fibers, pigment dispersants, film-forming aids, antifreeze agents, drying regulators, plasticizers, matting agents, matting agents. Examples include foaming agents, ultraviolet absorbers, antioxidants, light stabilizers, antifungal agents, and preservatives.

The method for dispersing the colored paint in a granular form is not particularly limited, and a known method can be adopted. Specifically, a method of dispersing a colored paint in an aqueous dispersion medium containing a dispersion stabilizer or the like can be employed.
The dispersion stabilizer is a component that stabilizes the colored paint in a granular form, and can be selected according to the type of the colored paint. Specific examples of the dispersion stabilizer include, for example, a component that acts as a crosslinking agent for a colored paint. Examples of such components include epoxies, isocyanates, amines, alkoxysilanes, organic titanates, aluminum chelates, magnesium salts, calcium salts, barium salts, aluminum salts, sodium salts, potassium salts, boron Examples include acid salts and phosphates. Other dispersion stabilizers include polyvinyl alcohol, polyacrylic acid, polyethylene oxide, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, casein, cellulose acetate phthalate, bentonite, gelatin, sodium alginate, gum arabic, pectin, xanthan gum, starch Etc. can also be used.

The particle diameter and shape of the color particles can be set as appropriate. Specifically, the shape of the stirring blade at the time of manufacture, the size and position of the stirring blade with respect to the stirring tank, the rotation speed of the stirring blade, the viscosity of the colored paint, the method and concentration of the dispersion stabilizer, the viscosity of the aqueous dispersion medium, etc. What is necessary is just to select and adjust suitably.
Although the particle diameter of a color grain is not specifically limited, Usually, it is about 0.01-10 mm (preferably 0.1-5 mm).

For example, spray coating, roller coating, brush coating, or the like can be employed as a method for applying the multicolored paint. When a concavo-convex pattern is expressed using a multicolored paint, a desired concavo-convex pattern may be formed with an undercoat material, and then a multicolored paint may be applied. For example, as described in JP-A-8-173899 A method etc. can be adopted. Further, a tile-like pattern, a geometric pattern, or the like can be formed using a joint rod, a joint form frame, or the like.
The application amount of the multicolor paint is usually about 0.2 to 1 kg / m ² . At the time of application, the viscosity can be appropriately adjusted by mixing a diluent such as water. The dilution ratio is usually about 0 to 10% by weight. The multicolored paint is usually dried at room temperature.

[Thin finish coating material / Thick finish coating material]
The thin finish coating material and thick finish coating material specified in JIS A6909 use a synthetic resin emulsion as a binder, and color pigments, extender pigments, aggregates, and other admixtures (dispersants, thickeners). , Antifoaming agent, preservative, etc.)

  Among these, as the synthetic resin emulsion, for example, vinyl acetate resin, epoxy resin, silicone resin, acrylic resin, urethane resin, acrylic urethane resin, acrylic silicon resin, fluorine resin, or a composite system thereof can be used. .

  Examples of color pigments include titanium oxide, zinc oxide, carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red potato, molybdate orange, permanent red, and permanent. Carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine Violet or the like can be used. A desired color can be expressed by using one or more of these in combination. The mixing ratio of the color pigment is usually about 1 to 300 parts by weight (preferably 2 to 200 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

  The extender pigment mainly acts as a filler, and is an effective component for forming a thick film. Specific examples of extender pigments include heavy calcium carbonate, light calcium carbonate, kaolin, clay, porcelain clay, china clay, diatomaceous earth, hydrous finely divided silicic acid, talc, barite powder, barium sulfate, precipitated barium sulfate, barium carbonate, carbonate Examples include magnesium, silica powder, and aluminum hydroxide. The particle size of the extender pigment is usually less than 50 μm (preferably 0.5 μm or more and less than 50 μm). The mixing ratio of the extender pigment is usually about 10 to 1000 parts by weight (preferably 20 to 500 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

  As the aggregate, for example, cryolite, feldspar, limestone, silica stone, silica sand, crushed stone, mica, siliceous shale, and pulverized products thereof, glass beads, resin beads, rubber particles, metal particles and the like can be used. The particle diameter of such aggregate is usually 0.05 to 5 mm. The mixing ratio of the aggregate is usually about 10 to 2000 parts by weight (preferably 30 to 1500 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin emulsion.

In the coating of such coating materials, various types of uneven patterns, such as sand wall, yuzu skin, fiber wall, ripple, stucco, uneven, can be selected by appropriately selecting the type of coating equipment and its usage. A pattern such as a lunar surface, a comb-like shape, or a worm-like shape can be formed. For example, a spray, a roller, a trowel, or the like can be used as the coating instrument. At this time, various uneven patterns can be formed by treating the coated surface with a design roller, a trowel, a brush, a comb, a spatula, or the like before the coating material is dried. Tile patterns, geometric patterns, etc. can be formed by using joint rods or joint molds. It is also possible to form a multicolor pattern by combining two or more kinds of coating materials having different colors.
The coating amount is usually about 0.3 to 10 kg / m ² although it depends on the type of pattern to be formed. At the time of application, a diluent such as water can be mixed to appropriately adjust the viscosity of the coating material. The dilution ratio is usually about 0 to 10% by weight. Drying is usually performed at room temperature.

[3] Water-based clear paint In the present invention, the water-based clear paint is applied after the above-mentioned decorative coating material is dried. The aqueous clear coating material in the present invention has a synthetic resin emulsion (A) having a pH of 4.0 or more and 10.0 or less, and a particle size of 1 to 200 nm and a pH of 5.0 or more and less than 8.5. The basic silica sol (B) is an essential component.

  The component (A) constituting the aqueous clear coating is a synthetic resin emulsion (hereinafter referred to as “component (A)”) having a pH of 4.0 or more and 10.0 or less. This component (A) acts as a binder.

  The pH of the component (A) is usually 4.0 or more and 10.0 or less, preferably 5.0 or more and 9.5 or less, more preferably 6.0 or more and 9.0 or less, and still more preferably 7.0 or more and 8.5. It is as follows. By using the component (A) having such a pH, good stability can be ensured when the component (B) described later is mixed. When the pH is out of the above range, when the component (A) and the component (B) are mixed, aggregates are generated or the viscosity of the paint increases in a short time. In extreme cases, the paint may gel.

  As the component (A), various synthetic resin emulsions can be used as long as the pH is within the above range. Specific examples include acrylic resin emulsions, acrylic silicon resin emulsions, fluororesin emulsions, and urethane resin emulsions.

[Acrylic resin emulsion]
As the acrylic resin emulsion, those obtained by radical copolymerization with an acrylic monomer and another monomer copolymerizable with the acrylic monomer can be used.

  The acrylic monomer is not particularly limited. For example, methyl (meth) acrylate (indicating that it is either methyl acrylate or methyl methacrylate; the same applies hereinafter), ethyl (meth) acrylate, and n-butyl. Alkyl group-containing (meth) acrylic monomers such as (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate and the like Hydroxyl group-containing (meth) acrylic monomers; (meth) acrylic acid and other ethylenically unsaturated carboxylic acids; dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate and other amino group-containing (meth) acrylic monomers Monomer; (Meth) acrylic Amide-containing (meth) acrylic monomers such as ethyl (meth) acrylamide; Nitrile group-containing (meth) acrylic monomers such as acrylonitrile; Epoxy group-containing (meth) acrylic monomers such as glycidyl (meth) acrylate Examples include a polymer.

  Other monomers that can be copolymerized with acrylic monomers include aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene, and vinyl toluene; maleic acid, itaconic acid, crotonic acid, fumaric acid Α, β-ethylenically unsaturated carboxylic acids such as acid and citraconic acid; sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl chloride; Chlorine-containing monomers such as vinylidene chloride and chloroprene; hydroxyl-containing alkyl vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether; alkylene glycol mono such as ethylene glycol monoallyl ether and propylene glycol monoallyl ether diethylene glycol monoallyl ether Allyl ethers; α-olefins such as ethylene, propylene and isobutylene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; Ethyl allyl ether And allyl ethers such as butyl allyl ether.

  When an acrylic resin emulsion is used as the synthetic resin emulsion, it is advantageous in that it has excellent durability, cost, and flexibility in resin design.

[Acrylic silicone resin emulsion]
As the acrylic silicon resin emulsion, those obtained by radical copolymerization of a silicon-containing acrylic monomer and another monomer copolymerizable with the silicon-containing acrylic monomer can be used.

  The silicon-containing acrylic monomer is not particularly limited. For example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyl Examples include hydrolyzable silyl group-containing vinyl monomers such as dimethoxysilane and γ- (meth) acryloxypropylmethyldiethoxysilane.

  As another monomer copolymerizable with the silicon-containing acrylic monomer, for example, a monomer used in the above-mentioned acrylic resin emulsion can be used without any particular limitation.

  When an acrylic silicon resin emulsion is used as the synthetic resin emulsion, it is advantageous in that it has excellent weather resistance, yellowing resistance, durability, chemical resistance, stain resistance, and the like.

[Fluororesin emulsion]
As the fluororesin emulsion, those obtained by radical copolymerization of a fluorine-containing monomer and another monomer copolymerizable with the fluorine-containing monomer can be used.

  Examples of the fluorine-containing monomer include fluoroolefins such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoroethylene, and hexafluoropropylene; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, Examples include fluorine-containing (meth) acrylates such as perfluorocyclohexyl (meth) acrylate.

  As another monomer copolymerizable with the fluorine-containing monomer, for example, monomers used in the above-mentioned acrylic resin emulsion can be used without any particular limitation.

  When a fluororesin emulsion is used as the synthetic resin emulsion, it is advantageous in that it has excellent weather resistance, yellowing resistance, durability, chemical resistance, stain resistance, and the like.

[Urethane resin emulsion]
The urethane resin-based emulsion is a generic term for an emulsion having urethane bonds in the coating film after the coating film is formed. That is, it may have a urethane bond before the coating film is formed, or may form a urethane bridge by a reaction after the coating film is formed. The form of the emulsion may be a one-pack type or a two-pack type.
As a one-pack type, a polymerizable monomer having a urethane bond is copolymerized with another copolymerizable monomer, and a polymerizable unsaturated monomer is polymerized in the presence of an aqueous resin having a urethane bond. And a method of mixing an aqueous urethane resin having a reactive group with an emulsion containing a group capable of reacting with the reactive group.
Examples of the two-component type include a combination of a water-dispersible isocyanate and a hydroxyl group-containing emulsion.

  When a urethane resin emulsion is used as the synthetic resin emulsion, it is advantageous in that it has excellent durability, solvent resistance, chemical resistance, stain resistance, and the like.

[Other cross-linking emulsions]
In the synthetic resin emulsion, in addition to the crosslinking reaction by the hydroxyl group and isocyanate compound, carbonyl group and hydrazide group, carboxylic acid and metal ion, epoxy group and amine, epoxy group and carboxyl group, carboxylic acid and aziridine, carboxylic acid and It is also possible to use an emulsion that forms a crosslinking reaction using carbodiimide, carboxylic acid and oxazoline, acetoacetate and ketimine, or the like. The crosslinking reaction type emulsion may be a one-component type or a multi-component type having two or more components.

  When a cross-linked emulsion is used as the synthetic resin emulsion, it is advantageous in that it has excellent durability, solvent resistance, chemical resistance, stain resistance, and the like.

  (A) A component can be manufactured by a well-known method, as long as the above-mentioned conditions are satisfied. For example, it can be produced by emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, oxidation-reduction polymerization or the like in an aqueous medium, and can also be produced by multistage polymerization as necessary. At this time, if necessary, an emulsifier, an initiator, a dispersant, a chain transfer agent, a buffering agent, or other additives or the like can be appropriately used.

  Component (B) in the aqueous clear coating is a neutral silica sol (hereinafter referred to as “component (B)”) having a particle size of 1 to 200 nm and a pH of 5.0 or more and less than 8.5.

  The particles constituting the component (B) are formed by hydrolytic condensation of silicate, and are composed of silica and have a high hardness and a silanol group (Si-OH) on the particle surface. is there. In the present invention, excellent contamination resistance can be exhibited by such a synergistic action of the hardness of the component particle (B) and the surface functional group. Although the specific mechanism of action is not clear, it is presumed that the component (B) is oriented on the surface of the coating film during the formation of the coating film, increasing the hardness and hydrophilicity of the coating film surface.

  The particle size of the component (B) is usually 1 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 50 nm, and still more preferably 20 to 40 nm as the primary particle size. When the particle diameter is too large, there is a risk of adversely affecting the appearance of the formed coating film, for example, the sharpness of the coating film is impaired. When the particle size is too small, there is a possibility that a sufficient effect cannot be obtained in the stain resistance. (B) The average primary particle diameter of a component is 5-100 nm, More preferably, it is 10-50 nm, More preferably, it is 20-40 nm. In the present invention, the antifouling effect can be enhanced by using two or more neutral silica sols (B) having different average primary particle sizes. The particle diameter of the component (B) is a value measured by a light scattering method.

  The pH of the component (B) needs to be 5.0 or more and less than 8.5, preferably 6.0 or more and less than 8.5, and more preferably 6.5 or more and 8.0 or less. Preferably, it is 7.0 or more and 8.0 or less. If the component (B) is adjusted to such a pH, an excellent antifouling effect is exhibited by the silanol group on the particle surface. When the pH is outside the above range, the stain resistance is insufficient, and it is disadvantageous in terms of water resistance and weather resistance.

Colloidal silica is mentioned as being similar to the component (B) in the present invention. Ordinary colloidal silica is roughly classified into an acidic type having a pH of 2 to 4 and an alkaline type having a pH of 9 to 11. On the surface of these colloidal silica particles, Si—OH is dissociated. Specifically, the particle surface of the acidic type colloidal silica is Si—O ⁻ .H ⁺ . Alkaline type colloidal silica, the particle surface ^Si-O - and Na-type is · Na ^{+, Si-O} - are classified into NH ₄ form a · _NH ^{4 +.}

  On the other hand, the component (B) in the present invention is in a state in which most of the Si—OH remains without dissociating on the particle surface, and is a compound different from the colloidal silica. In the present invention, it is presumed that excellent anti-contamination performance is exhibited by the particle surface characteristics of the component (B).

  As the component (B), those having an electric conductivity of 3 mS / cm or less (preferably 2 mS / cm or less, more preferably 1 mS / cm or less) are suitable. In addition, the electrical conductivity said here is a value measured using "Model SC82 personal SC meter SC8221-J" (made by Yokogawa Electric Corporation) (measurement temperature 25 degreeC).

  By using such a component (B), the water resistance and stain resistance of the formed coating film can be further enhanced.

  The component (B) can be produced using a silicate compound as a raw material. Examples of the silicate compound include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra t-butoxysilane, tetra Examples thereof include phenoxysilane and the condensates thereof. In addition, alkoxysilane compounds such as dimethoxydiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, and diethyldimethoxysilane can also be used together. A catalyst etc. can also be used at the time of manufacture. Moreover, the metal contained in a catalyst etc. can also be removed by an ion exchange process etc. after a manufacture process or after manufacture.

  As the medium for the component (B), water and / or a water-soluble solvent can be used. Examples of the water-soluble solvent include alcohols, glycols, glycol ethers and the like. In the present invention, it is particularly desirable that the medium is composed only of water. By using such a component (B), it is possible to reduce the volatile organic solvent (low VOC) of the paint. Moreover, the aggregate generation | occurrence | production at the time of mixing with (A) component can also be suppressed.

  The solid content of the component (B) is usually 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 30% by weight. If the solid content of the component (B) is within such a range, the stability of the component (B) itself, and the stability when the component (A) and the component (B) are mixed can be ensured. . If the solid content is too large, the component (B) itself may become unstable, or the coating material may become unstable when mixed with the component (A). If the solid content is too small, a large amount of component (B) must be mixed in order to obtain a sufficient anti-staining effect, which is not practical in terms of paint design.

  As the component (B) in the water-based clear coating, a neutral silica sol subjected to a hydrophobic treatment (hereinafter referred to as “component (B-1)”) is suitable. By using such a component (B-1), the stain resistance can be further enhanced.

  The hydrophobization treatment is desirably performed by combining a compound having at least one functional group selected from an alkoxyl group and a hydroxyl group (hereinafter referred to as “(p) component”) with the neutral silica sol.

  The component (p) can be used without limitation as long as it is a compound having a hydrophobic effect of neutral silica sol. For example, the following compounds are exemplified.

  1) Alkoxysilane compound; tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, tetraphenoxy Silane, dimethoxydiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxy Silane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxylane, butyltriethoxysilane, Rutripropoxysilane, butyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethylsilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, hexyltrimethoxy Silane, hexyltriethoxysilane, hexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxy Silane etc.

  2) Alcohols: methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, 2-ethyl-1-hexanol, n-heptanol, isoheptyl alcohol, n-octanol 2-octanol, n-nonanol, n-decanol, n-undecyl alcohol, n-dodecyl alcohol, 1-3 butanediol, 1-5 pentanediol, diacetone alcohol and the like.

  3) Glycols; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and the like.

  4) Glycol ethers: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monoethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether and the like.

  5) Fluorine alcohols; trifluoroethanol, pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, nonafluoro-t-butyl alcohol, 1 , 1,3,3-tetrafluoroisopropanol, 1,1-bis (trifluoromethyl) ethanol, 1,1,1,3,3,4,4,4-octafluoro-2-butanol, 2,2, 3,3,3-pentafluoro-1,1-bis (trifluoromethyl) propanol, 2,2,2-trifluoro-1- (trifluoromethyl) -1-tolylethanol and the like.

  Among the compounds exemplified above, fluorine alcohol is particularly preferable as the component (p).

  The component (p) is 0.01 to 50 parts by weight (preferably 0.02 to 30 parts by weight, more preferably 0.05 to 10 parts by weight) with respect to 100 parts by weight of the solid content of the neutral silica sol. It is desirable to mix. With such a ratio, the contamination resistance can be sufficiently enhanced.

  When the component (p) is mixed with the neutral silica sol, the component (p) may be diluted with water or a water-soluble solvent as necessary. When the component (p) and the neutral silica sol (B) are mixed and subjected to a hydrophobic treatment, a catalyst may be used as necessary.

  When the neutral silica sol is hydrophobized with the component (p), the hydrophobization treatment can be performed by combining the neutral silica sol with a product obtained by mixing the silane coupling agent with the component (p). . Alternatively, the neutral silica sol can be hydrophobized by mixing the component (p) after treating with a silane coupling agent. In such a case, a silane coupling agent having a functional group capable of reacting with the component (p) can be used as the silane coupling agent. For example, when the component (p) is a fluorine alcohol, an amino group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, or the like can be used.

  As for the temperature at the time of mixing and processing the neutral silica sol (B) and the (p) component, the lower limit is 10 ° C. or higher, preferably 20 ° C. or higher, more preferably 40 ° C. or higher, and the upper limit is It is desirable to set the temperature to about 200 ° C. or less, preferably 120 ° C. or less, more preferably 100 ° C. or less. By such temperature setting, the reactivity between the component (p) and the neutral silica sol is increased, which is preferable in terms of the expression of the antifouling effect. The heating time is not particularly limited, but is usually about 1 to 24 hours.

  In the present invention, contamination resistance can be enhanced by using a neutral silica sol in which a polyoxyalkylene group-containing compound is combined. As the polyoxyalkylene group-containing compound (hereinafter referred to as “component (q)”), a compound having at least one functional group selected from an alkoxyl group and a hydroxyl group and a polyoxyalkylene group is suitable.

  Examples of such component (q) include polyoxyethylene glycol, polyoxyethylene glycol monoalkyl ether, polyoxyethylene-propylene glycol, polyoxyethylene-tetramethylene glycol, polyoxyethylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, polyoxyethylene diglycolic acid, polyoxyethylene glycol vinyl ether, polyoxyethylene glycol allyl ether, polyoxyethylene glycol diallyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, Examples include polyoxyethylene alkylamine. (Q) The average molecular weight of a component should just be about 150-2000 normally.

  In order to combine the (q) component with the neutral silica sol, the neutral silica sol and the (q) component may be mixed and heated as necessary. The mixing ratio of the component (q) is 0.01 to 50 parts by weight (preferably 0.02 to 30 parts by weight, more preferably 0.05 to 10 parts by weight) with respect to 100 parts by weight of the solid content of the neutral silica sol. It is desirable to set the ratio. As for the temperature during heating, the lower limit is set to 10 ° C. or higher (preferably 20 ° C. or higher, more preferably 40 ° C. or higher), and the upper limit is set to 200 ° C. or lower (preferably 120 ° C. or lower, more preferably 100 ° C. or lower). Good. The heating time is not particularly limited, but is usually about 1 to 24 hours.

  The component (B) in the water-based clear coating is particularly preferably a neutral silica sol that has been subjected to a hydrophobization treatment and is combined with the polyoxyalkylene group-containing compound (q). If such a neutral silica sol is used, the stain resistance of the formed coating film can be further enhanced.

  As the component (B), when two or more neutral silica sols having different average primary particle diameters are used, it is desirable that at least one of them be hydrophobized. Furthermore, it is more desirable that at least one of the components is subjected to a hydrophobization treatment and is combined with the component (q).

  The mixing ratio of the component (B) in the aqueous clear coating material of the present invention is usually 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight in terms of solids with respect to 100 parts by weight of the solids of the component (A). Parts, more preferably 1 to 15 parts by weight. With such a mixing ratio, the effects of the present invention can be sufficiently exerted. When the amount of the component (B) is too small, sufficient contamination resistance cannot be obtained. (B) When there are too many components, it becomes easy to produce a crack in a coating film. In addition, the sharpness of the coating film tends to decrease.

The water-based clear paint of the present invention can be mixed with various components that can be used in ordinary paints as long as the effects of the present invention are not significantly impaired. Such components include, for example, film-forming aids, plasticizers, antifreeze agents, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, dispersants, thickeners, leveling agents, wetting agents, pH adjusting agents. Agents, matting agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents and the like.
In addition, the water-based clear paint of the present invention can be colored by mixing with a color pigment or the like as required. However, the degree of coloring must be suppressed to such an extent that the design of the decorative coating material is not impaired.

Various methods such as spray coating, roller coating, and brush coating can be employed as a method for applying the water-based clear paint of the present invention. The coating amount at the time of coating is usually about 0.1 to 0.5 kg / m ² . At the time of application, the viscosity of the paint can be appropriately adjusted by diluting with water or the like. The dilution ratio is usually about 0 to 20% by weight. The drying after applying the water-based clear paint may be usually performed at room temperature.

II. Decorative Laminate The present invention can also be applied to a decorative laminate in which a base material layer, a decorative layer, and a clear layer are laminated. Such a decorative laminated body can be suitably used as a plate-like building material for surface finishing such as a building or a civil engineering structure.

  Among these, as the base material layer, for example, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, asbestos cement board, ALC board, siding board, extrusion board, steel sheet, plastic board, gypsum board, plywood, woven Cloth, nonwoven fabric, ceramic paper, synthetic paper, glass cloth, mesh, etc. can be used. Moreover, the coating-film layer which consists of various coating materials can also be used as a base material layer. In the present invention, it is sufficient that at least one base material layer is included, and two or more base material layers may be included. The base material layer should just be laminated | stacked in the back surface side or decoration layer of a decoration layer, and may be sandwiched by the decoration layer.

The decoration layer should just have a multicolor pattern or an uneven | corrugated pattern. Such a decorative layer is formed by, for example, the above-described decorative coating material (stone-finish finish coating material, JIS K5667 multi-color paint, JIS A6909 thin finish coating material, thick finish coating material, etc.) Can be used. Moreover, what was obtained by shape | molding the composition comprised from a binder, a pigment, an aggregate, etc. can also be used.
The clear layer is formed by the above-mentioned water-based clear paint. This clear layer is laminated on the surface of the decorative layer.

As a method for producing the laminate of the present invention, a known method can be adopted, and for example, the following method can be adopted.
(I) The decorative coating material is poured into a mold, the base material layer is laminated and cured, and after curing, demolded, and an aqueous clear paint is applied to the surface of the decorative layer.
(Ii) A decorative coating material is applied to the base material layer, and then an aqueous clear paint is applied to the surface.

  As the mold used in the above (i), for example, a mold made of silicon resin, urethane resin, or the like, or a mold provided with release paper can be used. In the method (i), since the mold frame side is the surface of the laminate, a desired uneven pattern can be imparted to the laminate surface by adjusting the shape inside the mold. In the method (i), a method using a means such as a spray, a trowel, a reciprocator, or a coater can be employed instead of pouring.

The dimensions of the decorative laminate can be adjusted by appropriately cutting after laminating each layer. In the above method (i), it is also possible to manufacture using a mold having dimensions determined in advance without cutting the manufactured laminate.
Although the thickness of each layer which comprises a decoration laminated body is not specifically limited, Usually, a base material layer is about 0.1-10 mm, a decoration layer is about 0.1-10 mm, and a clear layer is about 10-300 micrometers.

Specifically, the decorative laminate of the present invention can be applied to inner and outer walls, partitions, doors, ceilings, pillars, and the like in houses, apartments, schools, hospitals, stores, offices, factories, warehouses, restaurants, and the like. What is necessary is just to stick using an adhesive agent, an adhesive, an adhesive tape, a nail, a hook, etc. when constructing this invention laminated body in such a site | part. In addition, it can also be fixed using pins, fasteners, rails or the like.
Moreover, you may cut | disconnect and use a laminated body for arbitrary shapes at the time of construction. In this case, the side surface of the laminate after cutting can be appropriately treated with a paint or the like.

  Examples are given below to clarify the features of the present invention.

<Manufacture of decorative coating materials>
For 200 parts by weight of acrylic resin emulsion (methyl methacrylate-styrene- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 7.8, solid content 50 wt%, minimum film forming temperature 25 ° C.) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) 18 parts by weight, polyurethane-based thickener 5 parts by weight, silicone-based antifoaming agent 3 parts by weight, coloring with particle diameter 0.1-2 mm Decorative coating material A was produced by uniformly mixing 520 parts by weight of the aggregate mixture (white: grey: black = 3: 3: 1) by a conventional method.

<Manufacture of water-based clear paint>
According to the formulation shown in Table 1, each raw material was uniformly mixed by a conventional method to produce a coating material. The compounding amounts in Table 1 are expressed in parts by weight. The following raw materials were used in the production of the water-based clear paint.
Resin: acrylic resin emulsion (methyl methacrylate-cyclohexyl methacrylate- (2-ethylhexyl acrylate) -methacrylic acid copolymer, pH 7.3, solid content 50% by weight, minimum film-forming temperature 28 ° C.)
・ Film forming aid: Propylene glycol monobutyl ether ・ Thickener: Polyurethane thickener ・ Defoamer: Silicone defoamer ・ Low fouling agent A: Neutral silica sol (pH 7.6, solid content 20% by weight) Average particle size 27 nm, electrical conductivity 0.6 mS / cm)
・ Low pollution agent B: See Synthesis Example 1 ・ Low pollution agent C: See Synthesis Example 2 ・ Low pollution agent D: See Synthesis Example 3 ・ Low pollution agent E: See Synthesis Example 4 ・ Low pollution agent F : See Synthesis Example 5 Low-polluting agent G: Neutral silica sol (pH 7.8, solid content 12% by weight, average primary particle size 12 nm, electrical conductivity 0.3 mS / cm)
・ Low pollution agent H: basic colloidal silica (pH 9.5, solid content 20% by weight, average primary particle size 20 nm, electric conductivity 1.7 mS / cm)
・ Low pollution agent I: ethyl silicate condensate (average molecular weight 750)
・ Catalyst: Dibutyltin dilaurate

(Synthesis Example 1)
Into a reaction vessel equipped with a reflux condenser and a stirring blade, 500 parts by weight of the low contamination agent A was charged, and 0.3 parts by weight of trifluoroethanol was gradually added dropwise with stirring. Subsequently, after heating up to 80 degreeC and continuing stirring for 24 hours, it stood to cool to room temperature and obtained the low pollution agent B.

(Synthesis Example 2)
In a reaction vessel equipped with a reflux condenser and a stirring blade, 500 parts by weight of the low-contaminating agent A was charged, and 1.0 part by weight of tetramethoxysilane was gradually added dropwise with stirring. Subsequently, after heating up to 80 degreeC and continuing stirring for 24 hours, it stood to cool to room temperature and obtained the low pollution agent C.

(Synthesis Example 3)
Into a reaction vessel equipped with a reflux condenser and a stirring blade, 500 parts by weight of the low contamination agent A was charged, and 1.0 part by weight of methyltrimethoxysilane was gradually added dropwise with stirring. Subsequently, after heating up to 80 degreeC and continuing stirring for 24 hours, it stood to cool to room temperature and obtained the low pollution agent D.

(Synthesis Example 4)
A reaction vessel equipped with a reflux condenser and a stirring blade was charged with 500 parts by weight of the low-contaminating agent A, 0.3 parts by weight of trifluoroethanol was gradually added dropwise with stirring, and then 0.15 parts by weight of methoxypolyethylene glycol. Was gradually added dropwise. Subsequently, after heating up to 80 degreeC and continuing stirring for 24 hours, it stood to cool to room temperature and obtained the low pollution agent E.

(Synthesis Example 5)
A reaction vessel equipped with a reflux condenser and stirring blades was charged with 500 parts by weight of the low-contaminating agent A, and 0.3 parts by weight of trifluoroethanol and 0.3 parts by weight of γ-aminopropyltrimethoxysilane while stirring. The mixed solution was gradually added dropwise. Subsequently, after heating up to 80 degreeC and continuing stirring for 24 hours, it stood to cool to room temperature and obtained the low pollution agent F.

<Test method>
A 300 × 150 × 3 mm aluminum plate bent at a third position from the upper end so that the inner angle was 135 degrees was used as a test substrate. After spraying SK # 1000 primer at a coating amount of 0.15 kg / m ² on the convex surface of the test substrate and drying for 8 hours in a standard state, spray the decorative coating material A at a coating amount of 4 kg / m ² . It was painted and cured for 24 hours under standard conditions. Next, the aqueous clear paint obtained by the above method was spray-coated at a coating amount of 0.3 kg / m ² and dried and cured in a standard state for 7 days.
The finished appearance of the specimen obtained by the above method was confirmed visually. In the evaluation, “Good” indicates that the sharpness is good, and “No” indicates that the cloudiness is low and the sharpness is low.
Next, the specimen was installed in the Ibaraki city, Osaka, facing the south side with the wide surface of the specimen vertical, and exposed outdoors for 3 months. At this time, the contamination state on the vertical surface was visually observed, and the contamination resistance was evaluated in five stages (excellent: 5>4>3>2> 1: poor) according to the degree of contamination.

<Test results>
The test results are shown in Table 2. In Examples 1 to 7, good results could be obtained in any test.

(Example 8)
After applying a release agent to a silicone resin mold having a rock-like surface pattern (length 150 mm x width 70 mm x depth 5 mm), pouring decorative coating material A, placing a mesh on it, roller The sample was lightly pressed and smoothed, dried at room temperature for 48 hours, and demolded. Subsequently, the surface was spray-coated with an aqueous clear paint G at a coating amount of 0.3 kg / m ² and dried and cured in a standard state for 7 days.
The decorative laminate obtained by the above method was tested by the above-described test method. As a result, the finished appearance was “◯” and the stain resistance was “5”.

Claims (4)

After applying a decorative coating material to the base material to form a multicolor pattern or uneven pattern,
Essential components are a synthetic resin emulsion (A) having a pH of 4.0 to 10.0 and a neutral silica sol (B) having a particle diameter of 1 to 200 nm and a pH of 5.0 to less than 8.5. And, based on 100 parts by weight of the solid content of the synthetic resin emulsion (A), an aqueous clear paint containing 0.1 to 50 parts by weight of the neutral silica sol (B) in terms of solid content is applied. How to finish the decorative surface.   2. The decorative surface coating finish method according to claim 1, wherein the neutral silica sol is subjected to a hydrophobic treatment. A decorative laminate having a base material layer, a decorative layer, and a clear layer,
The decorative layer has a multicolor pattern or an uneven pattern,
The clear layer has a synthetic resin emulsion (A) having a pH of 4.0 to 10.0, and a neutral silica sol having a particle diameter of 1 to 200 nm and a pH of 5.0 to less than 8.5 ( B) is an essential component, and is formed of an aqueous clear paint containing 0.1 to 50 parts by weight of the neutral silica sol (B) in terms of solids with respect to 100 parts by weight of the solids of the synthetic resin emulsion (A). A decorative laminate characterized in that the decorative laminate.   The decorative laminate according to claim 3, wherein the neutral silica sol has been subjected to a hydrophobic treatment.