JPH08281202A - Production of inorganic decorative board - Google Patents

Abstract

PURPOSE: To provide an inorg. decorative board having excellent design characteristics and durability by coating the surface of an inorg. base board with a primer coating material contg. pigments, then coating the surface thereof, wet on wet, with a finish coating material contg. color particles and transparent particles respectively having specific grain sizes. CONSTITUTION: The surface of the inorg. base material is coated with the primer coating material contg. the pigments and is then coated thereon, wet on wet, with the finish coating material contg. the color particles having the grain size of 20 to 360μm and the transparent particles having the grain size of <=250μm, by which the high design characteristics and long-term weather resistant performance are imparted to the base material. At this time, the mixing ratio of the color particles and the transparent particles is preferably 1:10 to 5:1. The design characteristics tend to degrade if the mixing ratio is off this range. The color particles and the transparent particles preferably occupy 3 to 60wt.% of the entire part of the solid content of the finish coating material in total weight. The scattered particles are hardly visible if the ratio is below 3wt.%. The primer coating film is no longer visible if the ratio exceeds 60wt.%. Further, the binder of the finish coating material is preferably an acrylic copolymer and others.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an inorganic decorative board which has excellent designability due to the presence of color particles in a coating film and has excellent durability.

[0002]

2. Description of the Related Art As a method for producing this kind of inorganic decorative board, the following production method has been known as a typical one. (A) A method of mixing silica sand or cold water sand into a paint containing an organic pigment to finish so as to give a ricin-like appearance, or a method of spreading color silica sand or mixing with clear paint to finish. (B) A method of mixing plastic beads or color particles of a specific particle size with a clear paint and finishing with airless spray or the like.

[0003]

However, in the above method (a), since the coating means is finished with a resin gun having a large diameter, it is suitable for coating buildings, but it is not suitable for mass production coating in factories. Has disadvantages such as low coating treatment capacity and difficulty in controlling the coating amount. In addition, as a remedy for this, in mass production coating in factories, a finishing method, etc., in which the above aggregate is sprinkled on an uncured coating film using a sand spreader and overlayed with a clear coating, is devised. It has the drawbacks of requiring a sand spreader and increasing the space of the coating line.

Further, the method (b) eliminates the drawbacks (b) and is suitable for mass production coating, but the durability of the obtained coating film is not sufficient, and repainting of buildings is not possible. When implemented, it was difficult to restore the appearance. Therefore, in view of the present circumstances, the present inventor, as a result of diligent studies to eliminate the above-mentioned drawbacks, as a result of limiting the particle component, carefully selecting a film-forming component having excellent weather resistance and overcoming the above-mentioned drawbacks. Then, the present invention has been reached.

[0005]

That is, the method for producing an inorganic decorative board of the present invention comprises applying an undercoat paint containing a pigment onto an inorganic substrate, and then applying color particles having a particle size of 20 to 360 μm and a particle size of 250 μm or less. It is characterized in that it has a high degree of designability and long-term weatherability by being repeatedly coated with a top-coat paint containing transparent particles.

The present invention will be described in detail below. In the present invention, as the undercoating paint, conventionally known general-purpose inorganic / organic coloring pigments, room temperature curing type paints including extender pigments, forced drying type and baking curing type coatings can be used. That is, the undercoat paint is a synthetic resin, a pigment and a solvent if necessary,
It may be a paint which is composed of additives, an improving agent and the like and which is in a completely concealed state, or a translucent or transparent color clear state in which the underlying substrate is visible in some cases.

The synthetic resin includes cellulose resin, vinyl resin, acrylic resin, amino acrylic resin,
Representative examples include acrylic urethane resin-based, polyester urethane resin-based, acrylic silicone resin-based and the like. Further, these synthetic resins can be arbitrarily selected from any of a type dissolved or dispersed in an organic solvent, a type dissolved or dispersed in water, a solventless type and a powder type.
Examples of the pigment include various inorganic / organic color pigments such as titanium oxide, iron oxide, carbon black, phthalocyanine, and quinacridone, and mica powder treated with aluminum powder, stainless powder, titanium oxide, and the like.
Further, as an extender pigment, if necessary, barium sulfate,
Various kinds of materials such as talc and kaolin can be used together.

Further, if necessary, a solvent such as water, xylene, toluene, butanol, methyl isobutyl ketone, butyl acetate, cellosolve, an ultraviolet absorber, a surface conditioner,
Various additives such as a curing accelerator, a suspending agent and a dispersant, a modifier and the like can be appropriately used.

The color particles used in the present invention are scattered on the finish coated surface and are an essential component in terms of design. Specifically, polyethylene-based, acrylic-based, urethane-based, polyester-based, melamine-based, phenol-based spherical or amorphous plastic beads colored with pigments, glass flake metal-plated products, and aluminum foil coated with color clear After that, it is punched or cut into particles, mica particles are metal-plated, or naturally colored mica powder, artificially colored mica powder, colored glass powder, colored glass beads, ceramic powder, aluminum flakes, stainless steel. Particles such as flakes and titanium oxide-treated mica powder. The particle size is 20-3
Those in the range of 60 μm can be appropriately used, and 40
A layer having a size of μm or more is preferable from the viewpoint of visibility, and 280
From the viewpoint of coating workability, those having a thickness of μm or less are preferable.

The transparent particles used in the present invention are
Combined with color particles, it has the function of giving a rough feeling on the finished coated surface, or adjusting the gloss,
Like color particles, it is an essential component in terms of design. Specifically, it is acrylic, urethane-based, polyester-based, polyethylene-based, melamine-based spherical or amorphous particles such as pigment-free plastic beads, and in some cases, talc, mica, calcium carbonate, oxidation It is also possible to use particle powders of mineral substances such as silicon and silicic anhydride together. Those having a particle diameter of 250 μm or less can be appropriately used, and those having a particle diameter of 220 μm or less are more preferable from the viewpoint of suitability for coating workability.

Further, the mixing ratio of the color particles and the transparent particles is preferably 1:10 to 5: 1, more preferably 1: 5 to 3: 1 and out of this mixing ratio range. In the case of (1), the scattered amount of the color particles is too small or too large, so that the designability tends to be poor.

The total amount of the color particles and the transparent particles is preferably 3 to 60% by weight, more preferably 5 to 50% by weight, based on the total solid content of the overcoating material. If the amount is less than 3% by weight, the scattered particles are difficult to visually recognize, and if the amount is more than 60% by weight, the undercoat film cannot be visually recognized and the design is poor.

As the binder of the top coating used in the present invention, an acrylic copolymer, a hydrolyzable silyl group-containing acrylic copolymer, a fluorine-containing copolymer, a hydrolyzable silyl group-containing fluorine-containing copolymer, and It is preferable to use at least one selected from the group consisting of alkoxysilane condensates.

The acrylic copolymer that can be used in the present invention includes methyl (meth) acrylate, ethyl (meth) acrylate, based on the total weight of the monomers to be copolymerized.
Butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate having a total weight of 70% or more are preferable in terms of resistance to ultraviolet ray deterioration. . Further, in order to exhibit higher weather resistance, a hindered amine group is added as a functional group to 0.5.
Content of 5 to 5% by weight, and 1 to 3 kinds of cyclohexyl (meth) acrylate, t-butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate in total weight are all monomers of the copolymer. More preferably, it accounts for 30% by weight or more of the weight. The acrylic copolymer having a number average molecular weight of 10,000 to 200,000 is preferably used. The copolymer is of a solvent evaporation drying type, or a curing type such as an aminoplast cross-linking thermosetting type and an isocyanate cross-linking drying type.

The hydrolyzable silyl group-containing acrylic copolymer that can be used in the present invention is an acrylic copolymer containing at least one hydrolyzable silyl group in the side chain in one molecule. Specifically, it can be copolymerized with an acrylic ester having a prime number of 1 to 6 of (meth) acrylic acid and an amount of 50% by weight or more (total amount) of all monomers constituting the copolymer. A copolymer having a monomer containing a hydrolyzable silyl group as an essential component and having a weight average molecular weight of 6,000 to 1
000, preferably 8,000 to 50,000
It is 0. The hydrolyzable silyl group-containing acrylic copolymer is condensation-crosslinked mainly with a curing catalyst such as an organic metal.

The fluorine-containing copolymer that can be used in the present invention is, for example, a solvent volatilization dry type, an aminoplast bake-curing type, an isocyanate cross-linking type developed as a coating resin described in JP-A-57-34107. There are curable types. The hydrolyzable silyl group-containing fluorocopolymer that can be used in the present invention is a fluorocopolymer having at least one hydrolyzable silyl group in the side chain in one molecule. Specifically, it is a copolymer having a fluoroolefin, an alkyl vinyl ether, and a monomer containing a hydrolyzable silyl group copolymerizable with the monomer as an essential component, and having a weight average molecular weight of 4,000 to 60. 1,000,
It is preferably 6,000 to 50,000, and condensation-crosslinking is mainly performed by a curing catalyst such as an organic metal.

The alkoxysilane condensate which can be used in the present invention has the general formula R-Si (OR ") ₃ (wherein R is a C ₁ -C ₅ alkyl group or a C ₁ -C ₄ acyl group). R'is a C ₁ -C ₈ alkyl group) or RR'Si (OR ") ₂ (wherein R is a C ₁ -C ₅ alkyl group and R'is C
_{1 to} C ₄ acyl group and R ″ is a C _{1 to} C ₈ alkyl group), which is a condensate of organoalkoxysilane having a weight average molecular weight of 400 to 100,000, preferably 1,500. To 12,000, which are condensed and crosslinked by a catalyst such as an organic metal, provided that both of them may be condensed by using a plurality of monomers, and R, R ', R " May not always have the same carbon number.

As the binder component, an acrylic copolymer, a hydrolyzable silyl group-containing acrylic copolymer, a fluorine-containing copolymer, a hydrolyzable silyl group-containing fluorine-containing copolymer or an alkoxysilane condensate is used alone. Although they may be used, within a compatible range, (A) an acrylic copolymer and a fluorine-containing copolymer, (B) a hydrolyzable silyl group-containing acrylic copolymer and a hydrolyzable silyl group-containing fluorine Copolymer, (C) Hydrolyzable silyl group-containing acrylic copolymer and alkoxysilane condensate, (D) Hydrolyzable silyl group-containing fluorine-containing copolymer and alkoxysilane condensate,
It is also possible to use (E) a combination of a hydrolyzable silyl group-containing acrylic copolymer, a hydrolyzable silyl group-containing fluorine-containing copolymer and an alkoxysilane condensate.

Further, various additives and modifiers can be appropriately mixed and used in the topcoat paint used in the present invention. As various additives and modifiers, there are dispersants, suspending agents, surface modifiers, ultraviolet absorbers, and water scavengers.
It can be used in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the solid content of the binder component.

A coating machine for spraying the thus-obtained top coating composition into a spray state by a conventional method such as air spray, airless spray, electrostatic coating or the like is preferably used. The present topcoat paint can be applied over the base paint film regardless of whether it is in the undried state or the dried state.
That is, when the base coating film is not dried yet, the top coating composition is coated again after a setting time of about 10 seconds to 10 minutes. In addition, when the base coating film is dried again after the base coating film is dried, when the base coating film is dried at room temperature, it is generally left after standing for 2 hours or more, or after forced drying, the coating is repeated and baked. In the case of a curable type, it is baked and cured, and then applied repeatedly. Drying conditions for the top coating are room temperature ~
In the temperature range of 180 ° C., it is 3 minutes to 24 hours. Moreover, mortar, concrete, ALC board, gypsum slag perlite board, wood chips, cement board, flexible board, calcium silicate board, inorganic base material and the like can be appropriately used as the article to which the present invention can be applied.

[0021]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Examples 1 to 8 and Comparative Examples 1 to 2 Using the base materials described in Tables 1 to 5, base coats, middle coats and top coats were performed using the coating materials, coating conditions and drying conditions described in Tables 1 to 5. . The coating compositions used in Examples and Comparative Examples were as follows. In addition, "parts" and "%" in Examples and Comparative Examples are shown based on weight.

<Undercoating paint a> A mixed agent solution (solid content 15.0%) of butyl acetate / xylene = 1/1 of a cooled diphenol methane diisocyanate compound. <Undercoating paint b> Acrylic copolymer consisting of methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate = 70/20/10: 10 parts, hexamethylene diisocyanate trimethylpropane adduct: 4 parts, tolylene diisocyanate trimer body: 3 parts, titanium White: 15 parts, kaolin: 8 parts, barium sulfate: 4 parts, butyl acetate: 20 parts, xylene: 28 parts.

<Intermediate coating paint a> Hydroxyl group-containing acrylic resin copolymer (Note 1): 3
0 parts, titanium white: 20 parts, iron oxide yellow: 0.1 parts iron oxide red rust: 0.05 parts, carbon black: 0.7 parts, precipitating barium sulfate: 16 parts, talc: 5 parts, butyl acetate: 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Intermediate coating b> Hydroxyl group-containing acrylic resin copolymer (Note 1): 3
0 part, titanium white: 40 parts, iron oxide yellow: 0.4 part, iron oxide red rust: 0.01 part, carbon black: 0.1 part, butyl acetate: 11 parts, toluene: 15 parts, yellow-free poly Isocyanate (Note 2): 3.5 parts.

<Intermediate coating c> Hydroxyl group-containing acrylic resin copolymer (Note 1): 3
0 parts, titanium white: 20 parts, iron oxide yellow: 0.77 parts, iron oxide red rust: 0.1 parts, carbon black: 0.26 parts, precipitating barium sulfate: 16 parts, talc: 5 parts, butyl acetate : 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Intermediate coating d> Hydroxyl group-containing acrylic resin copolymer (Note 1): 5
0 parts, titanium white: 20 parts, iron oxide yellow: 0.04 parts, carbon black: 0.02 parts, butyl acetate: 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 Department.

<Intermediate coating e> Highly weather resistant acrylic resin (Note 3): 30 parts, titanium white: 20 parts, iron oxide yellow: 0.8 part, iron oxide red rust: 0.05 part, carbon black: 0.0 27 parts, precipitating barium sulfate: 16 parts, talc: 5 parts, butyl acetate: 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Intermediate coating paint f> High weather resistance acrylic resin (Note 3): 30 parts, titanium white: 20 parts, iron oxide yellow: 1.32 parts, iron oxide red rust: 0.28 parts, carbon black: 0. 06 parts, precipitating barium sulfate: 16 parts, talc: 5 parts, butyl acetate: 9 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Intermediate coating paint g> Acrylic silicon varnish (Note 4): 30 parts, methyl orthoformate: 2 parts, titanium white: 20 parts, iron oxide yellow: 3.2 parts, iron oxide red rust: 0.5 parts, Carbon black: 0.1 part, precipitating barium sulfate: 13 parts, talc: 5 parts, butyl acetate: 10 parts, toluene: 15 parts, di-n-butyltin diacetate: 2 parts.

<Intermediate coating h> Acrylic silicon varnish (Note 4): 30 parts, titanium white: 20 parts, iron oxide yellow: 1.0 part, iron oxide red rust: 0.03 parts, carbon black: 0.07 parts Precipitable barium sulfate: 16 parts, talc: 5 parts, butyl acetate: 11 parts, toluene: 15 parts, di-n-butyltin diacetate: 2 parts.

<Intermediate paint i> High weather resistance acrylic resin (Note 3): 30 parts, titanium white: 20 parts, iron oxide yellow: 0.5 parts, carbon black: 0.15 parts, precipitable barium sulfate: 16 Parts, talc: 5 parts, butyl acetate: 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Intermediate coating paint j> High weather resistance acrylic resin (Note 3): 30 parts, titanium white: 20 parts, iron oxide yellow: 0.5 part, iron oxide red rust: 0.03 parts, carbon black: 0.0. 07 parts, talc: 5 parts, precipitating barium sulfate: 16 parts, butyl acetate: 10 parts, toluene: 15 parts, non-yellowing polyisocyanate (Note 2): 3.5 parts.

<Top coat 1> Acrylic varnish A (Note 5): 18.0 parts, Acrylic varnish B (Note 6): 37.0 parts, Acrylic beads (white) (Note A): 5.4 parts, Acrylic Beads (ki) (Note B): 2.5 parts, Acrylic beads (rust) (Note C): 0.2 parts, Acrylic beads (Black) (Note D): 1.0 parts, Acrylonitrile beads (Note a) : 4.0 parts, Acrylic beads A (Note b): 8.0 parts, Acrylic beads B (Note c): 9.0 parts, Precipitation inhibitor: 0.4 parts, Dispersant: 1.0 parts, Acetic acid Butyl: 6.0 parts, xylene: 7.5 parts, non-yellowing polyisocyanate (Note 2): 5.0 parts.

<Topcoat paint 2> High weather resistance acrylic resin (Note 3): 74.0 parts, metal coated glass flakes (Note E): 2.0 parts, polyethylene beads (Note d): 5.0 parts, anhydrous Silicic acid: 2.0 parts, precipitation inhibitor: 0.4 parts, dispersant: 1.0 parts, UV absorber: 0.6 parts, butyl acetate: 5.0 parts, xylene: 10.0 parts, yellow-free Modified polyisocyanate (Note 2): 5.0 parts.

<Topcoat 3> Acrylic silicon varnish (Note 4): 74.0 parts, Metal coated glass flakes (Note E): 2.0 parts, Mica (white) (Note F): 0.3 parts, Aluminum Punched foil (Note G): 0.2 parts, polyethylene beads (Note d): 5.0 parts, silicic anhydride: 2.0 parts, suspending agent: 0.4 parts, dispersant: 1.0 parts, UV absorber: 0.6 parts, butyl acetate: 5.0 parts, xylene: 9.5 parts, di-n-butyltin diacetate: 2.0 parts.

<Topcoat 4> Fluorine-containing copolymer (Note 7): 52.0 parts, acrylic beads (white) (Note A): 10.0 parts, acrylic beads (K) (Note B): 3. 8 parts, acrylic beads (rust) (Note C): 0.6 parts, aluminum foil color clear coated (black) punched product (Note H): 4.5 parts, acrylonitrile beads (Note a): 3.0 parts, Silicic anhydride: 3.5 parts, Precipitation inhibitor: 3.0 parts, Dispersant: 4.0 parts, Ultraviolet absorber: 0.6 parts, Methyl isobutyl ketone: 5.0 parts, Toluene: 6.0 parts, Xylene: 4.0 parts, non-yellowing polyisocyanate (Note 2): 5.0 parts.

<Topcoat 5> Alkoxysilane condensate (Note 8): 83.0 parts, acrylic beads (white) (Note A): 2.2 parts, acrylic beads (black) (Note D): 3.5 Parts, metal coated glass flakes (Note E): 0.6 parts, acrylic beads B (Note c): 3.0 parts, silicic acid anhydride: 0.6 parts, suspending agent: 1.5 parts, dispersant: 2 0.0 parts, toluene: 3.6 parts, di-n-butyltin diacetate: 2.0 parts.

<Top coat 6> Fluorine-containing copolymer (Note 7): 44 parts, Acrylic varnish C (Note 9): 15 parts, Mica (black) (Note 1): 2.2 parts, punched aluminum foil (Silver) (Note J): 0.3 parts, Acrylic beads A (Note b): 18.0 parts, Precipitation inhibitor: 3.0 parts, Dispersant: 4.0 parts, Ultraviolet absorber: 0.6 Parts, butyl acetate: 3.0 parts, xylene: 6.4 parts, non-yellowing polyisocyanate (Note 2): 5.0 parts.

<Topcoat 7> Hydrolyzable silyl group-containing fluorine-containing copolymer (Note 10):
52.0 parts, acrylic beads (white) (Note A): 13.0 parts, acrylic beads (ki) (Note B): 2.0 parts, acrylic beads (rust) (Note C): 0.4 parts, Aluminum foil color clear coated (black) punched product (Note H): 4.6 parts, acrylonitrile beads (Note a): 3.0 parts, silicic anhydride: 3.4 parts, precipitation inhibitor: 3.0 parts, dispersion Agent: 4.0 parts, UV absorber: 0.6 parts, Methyl isobutyl ketone: 5.0 parts, Toluene: 6.0 parts, Xylene: 3.0 parts, Di-n-butyltin diacetate: 2.0 parts. 0 copies.

<Topcoat paint 8> Acrylic varnish containing hydrolyzable silyl group (Note 11):
17.0 parts, hydrolyzable silyl group-containing fluorine-containing copolymer (Note 10):
35.0 parts, stamped aluminum foil (silver) (Note J): 0.3 parts, aluminum foil color clear coating (bronze) Stamped product (note K): 0.3 parts, aluminum foil color clear coating (black) Punched product (Note H): 3.0 parts, Acrylonitrile beads (Note a): 3.5 parts, Acrylic beads A (Note b): 15.0 parts, Silicic anhydride: 3.4 parts, Precipitation inhibitor: 3 0.0 parts, dispersant: 4.0 parts, ultraviolet absorber: 0.6 parts, methyl isobutyl ketone: 5.0 parts, toluene: 6.0 parts, xylene: 4.0 parts, di-n-butyltin. Diacetate: 2.0 parts.

<Top coat 9> Acrylic varnish A (Note 5): 18.0 parts, Acrylic varnish B (Note 6): 37.0 parts, Acrylonitrile beads (Note a): 4.0 parts, Acrylic beads A ( Note b): 13.0 parts, acrylic beads B (note c): 9.0 parts, silicic acid anhydride: 2.5 parts, suspending agent: 0.5 parts, dispersant: 1.0 part, butyl acetate: 6.0 parts, xylene: 9.0 parts, non-yellowing polyisocyanate (Note 2): 5.0 parts.

<Topcoat 10> Hydroxyl group-containing acrylic resin copolymer (Note 1): 7
4.0 parts, metal coated glass flakes (Note E): 2.0 parts, polyethylene beads (Note d): 5.0 parts, silicic anhydride: 2.0 parts, suspending agent: 0.6 parts, dispersant 1.0 part, ultraviolet absorber: 0.6 part, butyl acetate: 5.0 parts, xylene: 10.0 parts, non-yellowing polyisocyanate (Note 2): 7.0 parts.

<Description of Binder> (Note 1) Yupicacoat AC3402V (heating residue 50
%) [Trade name of Japan Yupika Co.]. (Note 2) Coronate HX (NCO content 20.5 to 22.0)
wt%) [trade name of Nippon Polyurethane Company]. (Note 3) U-Double 2816 (heating residue 46.5%)
[Product name of Nippon Shokubai Co., Ltd.]. (Note 4) Kaneka Zemlac YC3623 (heating residue 5
2.0%) [trade name manufactured by Kaneka Corporation]. (Note 5) Acridic 49-380 (heating residue 45.
0%) [trade name of Dainippon Ink and Chemicals, Inc.]. (Note 6) Altex L1043 (heating residue 40.0
%) [Trade name of Mitsui Toatsu Chemicals, Inc.]. (Note 7) Lumiflon LF200 (heating residue 59.0-6
1.5%) [Asahi Glass Co., Ltd. trade name]. (Note 8) Methyltrimethoxysilane: 100 parts, dimethyldimethoxysilane: 20 parts, ion-exchanged water: 25 parts, 0.1N hydrochloric acid water: 0.1 in a reaction vessel equipped with a reflux condenser and a stirrer. After adding and mixing 01 parts, the mixture was heated to 60 ° C. with stirring and reacted at the same temperature for 3 hours, isopropanol: 40 parts, ethylene glycol: 39
Parts, and cooled to give an organopolysiloxane solution having a weight average molecular weight of 1300 and a heating residue of 24.7%. (Note 9) A reaction vessel equipped with a reflux condenser and a stirrer was charged with xylol: 70 parts, and butyl acetate: 30 parts at 80 ° C.
The temperature is raised to 9 parts, methyl methacrylate: 9 parts, isobutyl methacrylate: 40 parts, ethylhexyl acrylate: 2
0 part, 2 hydroxyethyl methacrylate: 30 parts,
Acrylic acid: 1 part, Azobisisovaleronitrile:
1.5 parts of the mixture was added dropwise over 2 hours, azobisisovaleronitrile: 0.5 parts was added, the temperature was raised to 85 ° C., and the mixture was stirred and reacted for 4 hours. Nonvolatile content 50% weight average molecular weight 22000 Acrylic copolymer varnish of. (Note 10) Zeffle GK600 (heating residue 60.0%)
[Product name of Daikin Industries, Ltd.]. Roxyethyl: 30
Part, acrylic acid: 1 part, and azobisisovaleronitrile: 1.5 parts by dropwise addition over 2 hours, and then azobisisovaleronitrile: 0.5 part, and 85 ° C.
The temperature is raised to 4, and the mixture is stirred and reacted for 4 hours to obtain an acrylic copolymer varnish having a nonvolatile content of 50% and a weight average molecular weight of 22,000. (Note 10) Zeffle GK600 (heating residue 60.0%)
[Product name of Daikin Industries, Ltd.]. (Note 11) A reaction vessel equipped with a reflux condenser and a stirrer was charged with xylene: 90 parts, isopropanol: 10 parts, and heated to 80 ° C., methyl methacrylate: 23 parts, isobutyl methacrylate: 54 parts, , Γ-methacryloxypropyltriethoxysilane: 23 parts, and azobisisovaleronitrile: 1.5 parts were added dropwise over 2 hours, and azobisisovaleronitrile: 0.5 part was added to the mixture. The temperature was raised to ℃, and the mixture was reacted for 4 hours with stirring.
%, An acrylic copolymer varnish having a weight average molecular weight of 27,000.

<Description of Color Particles> (Note A) (acrylic fine particles, particle size 100 ± 10 μm
m). (Note B) (acrylic fine particles, particle size 100 ± 10μ
m). (Note C) (acrylic fine particles, particle size 100 ± 10μ
m). (Note D) (acrylic fine particles, particle size 100 ± 10μ
m). (Note E) (Metal-coated glass flakes, particle size 250μ
m). (Note F) (particle size 75 μm). (Note G) (particle size 200 μm ± 10). (Note H) (particle size 200 ± 10 μm). (Note I) (particle size 82 μm). (Note J) (particle size 200 μm ± 10). (Note K) (particle size 200 μm ± 10).

<Description of Transparent Particles> (Note a) (Polyacrylonitrile-based fine particles, particle size 23 ± 5
μm). (Note b) (acrylic fine particles, particle size 100 ± 10μ
m). (Note c) (crosslinked fine particles of methyl methacrylate, particle size 45 ±
3 μm). (Note d) (polyethylene wax dispersion, particle size 0 to 20 μm).

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

The decorative sheets obtained in Examples 1 to 8 and Comparative Examples 1 to 2 were evaluated in terms of designability, hardness, hot water resistance, weather resistance and freeze-thaw resistance according to the following methods. The results are shown in Table 6. <Test method> Designability: visual judgment O: Colored particles are scattered and excellent in designability x: Colored particles are not present and designability is poor Hardness: Pencil hardness measured according to JIS-K-5400 Warm water resistance: test piece The film was immersed in tap water at 60 ° C for 7 days, and the abnormality of the coating film was visually measured.

◯: No change Δ: Minor change such as decrease in gloss and whitening X: Large change such as decrease in gloss and whitening Weather resistance: Sunshine weather-O-meter 3000
Time ◯: No change in coating appearance, gloss retention of 90% or more Δ: Minor appearance of coating, gloss retention of 70% or more ×: Significant change of coating, gloss retention of 50% or more Freezing damage resistance : Measured by the ASTM-C666A method,
Number of cycles in parentheses ○: No crack generation △: Minor crack generation or peeling of coating film / part ×: Marked cracking, peeling of coating film

[0053]

[Table 6]

As shown in Table 6, Comparative Example 1 containing no color particles was inferior in designability, and Comparative Example 2 in which a normal acrylic resin was used as the binder in place of the high weather resistance acrylic resin, the designability was improved. Then, there is no problem, but the weather resistance is poor.

[0055]

INDUSTRIAL APPLICABILITY The inorganic decorative board obtained by the production method of the present invention has excellent designability and excellent durability due to the presence of color particles in the coating film.

Claims (4)

[Claims] 1. A design characterized in that an undercoat paint containing a pigment is applied onto an inorganic base material, and then an overcoat paint containing color particles having a particle size of 20 to 360 μm and transparent particles having a particle size of 250 μm or less is applied repeatedly. A method for producing an inorganic decorative board having excellent properties. 2. The method for manufacturing an inorganic decorative board according to claim 1, wherein the mixing ratio of the color particles and the transparent particles is 1:10 to 5: 1. 3. The method for producing an inorganic decorative board according to claim 1, wherein the total amount of the color particles and the transparent particles accounts for 3 to 60% by weight of the total solid content of the topcoat paint. 4. The binder of the topcoat paint is an acrylic copolymer, a hydrolyzable silyl group-containing acrylic copolymer, a fluorine-containing copolymer, a hydrolyzable silyl group-containing fluorine-containing copolymer, and an alkoxysilane condensation. It consists of at least 1 sort (s) chosen from the group which consists of a body, It is characterized by the above-mentioned.
Alternatively, the method for producing an inorganic decorative board according to the above item 3.