JPH1120112A - Decorative sheet having ultraviolet-curing coat formed thereon and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent blistering, scaling, etc., of a decorative sheet even when it is used as a member for a place where water is used, such as a bathroom or a kitchen, that is, a member exposed to such a severe condition that it is always in contact with heated drainage, and to enable suitable use of the sheet as that member. SOLUTION: This decorative sheet is manufactured by a method wherein a coat constituted of a coating composition containing a hydroxyl-containing acrylic polymer and a vinyl propionate polymer is formed on the surface of a base and wherein a prime coat constituted of the composition and a facing coat constituted of an ultraviolet-curing acrylate resin coating are formed in this sequence on the surface of the base. It is preferable that a vinyl chloride polymer is contained in this composition. The base is of an inorganic series preferably. After the coating composition is applied on the surface of the base, the ultraviolet-curing acrylate resin coating for facing is applied and cured on the surface of the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative plate having an ultraviolet-curable coating film formed thereon and a method for producing the same, and more specifically, for example, is always in contact with a water supply member such as a bathroom or a kitchen, or hot drainage. The present invention relates to a decorative plate with an ultraviolet-curable coating film, which does not swell or peel even when used as a member exposed to severe conditions, and which can be suitably used for a water supply member, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, members for water supply such as bathrooms and kitchens, and members exposed to severe conditions that are constantly in contact with hot wastewater are usually coated with a sealer on the surface of a base material and then primed. Apply and cure a solvent-based urethane resin paint for, on the undercoat film obtained, further, as compared to the solvent-based urethane resin paint for undercoat contains a relatively small amount of pigments and the like Apply a solvent-based urethane resin paint for top coating and apply hot air
The solvent-based urethane coating has been applied by a method such as heating and curing for about 0 to 40 minutes.

[0003] However, such a solvent-type urethane resin coating system using a solvent-type urethane resin coating for both upper and lower layers is excellent in warm water resistance and the like, but requires a long time for a hardening treatment at the time of construction, resulting in poor coating workability. There was room for improvement, such as inferiority.

In order to shorten the curing time, a UV-curable acrylate-based coating is applied after the above-mentioned solvent-based urethane resin coating for undercoating is applied, and UV irradiation is performed for a very short time (eg, about 10 seconds). )).

[0005] When the UV-curable acrylate paint is applied and cured after the undercoat solvent-based urethane resin paint is applied as described above, the coating workability is improved.
Poor adhesion between the undercoat layer and the topcoat layer of the obtained coating film, under severe conditions in contact with warm drainage such as in a bathroom, swelling of the coating film, peeling occurs in a relatively short time, There is a problem that the appearance is significantly impaired.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and is excellent in warm water resistance, hardness characteristics, meat feeling, stain resistance and the like. Decorative board, excellent in interlayer adhesion between coating layer, undercoat layer and topcoat layer, and suitable for use in bathrooms, kitchens, and other water-use members, and members exposed to harsh conditions. It is intended to provide boards.

An object of the present invention is to provide a simple method for producing the decorative board, which is excellent in warm water resistance, hardness characteristics, feeling of holding meat, stain resistance, and the like.

[0008]

SUMMARY OF THE INVENTION The decorative board according to the present invention comprises a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer (and a vinyl chloride polymer if necessary) on the surface of a substrate, preferably an inorganic substrate. It is characterized in that a coating film comprising a coating composition is formed.

In a preferred embodiment of the present invention, the surface of the above-mentioned base material, particularly the inorganic base material, contains a hydroxyl group-containing acrylic polymer, a vinyl propionate polymer and (if necessary, a vinyl chloride polymer). The undercoat film (a) described above consisting of a coating composition is formed, and a topcoat film (b) containing an ultraviolet-curable acrylate resin is further formed on the surface of the undercoat film (a). Is desirable.

In the method for producing a decorative plate according to the present invention, a polyisocyanate-based sealer is applied to the surface of a substrate, particularly an inorganic-based substrate, if necessary, and then a hydroxyl-containing acrylic polymer and a vinyl propionate-based polymer are applied. After applying (painting) a coating composition containing a polymer and (if necessary, a vinyl chloride-based polymer), an ultraviolet-curable acrylate resin paint is applied on the obtained coating film and cured. .

The decorative board with an ultraviolet-curable coating film according to the present invention, in particular, an inorganic decorative board, is resistant to warm water, has a hardness characteristic, a sense of solidity (that is, a heavy finish that looks like it is applied over and over again), Excellent contamination, etc., excellent adhesion between sealer and undercoat layer, undercoat layer and overcoat layer, etc. Even when used in places exposed to conditions, swelling and peeling do not occur, and it can be suitably used in these places.

In particular, a coating composition containing a hydroxyl group-containing acrylic polymer, a vinyl propionate polymer and, if necessary, a vinyl chloride polymer is applied to the surface of a substrate, and the resulting coating film ( When the UV curable acrylate resin paint is applied and cured on the undercoat film (undercoat layer) (a) to form the overcoat film (overcoat layer) (b), the decorative board of the present invention can be manufactured in a short time. Excellent adhesion (adhesion) between the undercoating film (a) and the overcoating film (b), such as water resistance, warm water resistance, hardness characteristics, feeling of holding, stain resistance, etc. The attached (inorganic) decorative board is particularly suitable as a water-running member or the like.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a decorative plate having an ultraviolet curable coating film according to the present invention and a method for producing the decorative plate will be described in detail.

<Decorative panel (inorganic decorative panel)> In the decorative panel according to the present invention, in particular, the inorganic decorative panel, a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer are further provided on the surface of the base material, if necessary. A coating film (a) composed of a coating composition containing a vinyl chloride polymer is formed.

The substrate (substrate to be coated) is not particularly limited, and may be made of an inorganic substrate such as slate, concrete, metal, calcium silicate, calcium carbonate, or autoclaved concrete; plastic, wood, or the like. Organic substrates; furthermore, these composite substrates;
A wood wool cement board and the like can be mentioned, and an inorganic base material is preferably used.

Examples of such a substrate with a coating film (a), that is, a decorative board, include an inner wall of a bathroom or a kitchen, an outer wall of a building, a panel, a curtain wall, and the like. Also,
The thickness (dry film thickness) of the coating film (a) is not particularly limited, but is usually 20 to 100 μm, preferably 30 to 60 μm.
It is about.

The material of the substrate, the material of the substrate,
A sealer, a binder, a primer, or the like is applied according to an application or the like, for example, in an amount such that the dry film thickness is about 30 to 200 μm, and the coating film (a) may be formed thereon. .

Examples of the sealer include conventionally known sealers. Preferably, the sealer is a polyisocyanate-based compound of a urethane curing agent described later [Examples: MDI, HDI,
HMDI etc.] are used.

In a preferred embodiment of the present invention, the above-mentioned coating film (undercoat film, undercoat layer) (a) and an ultraviolet-curable acrylate resin as described later are formed on the surface of a substrate, preferably an inorganic substrate. Paint film (top coat, top coat)
(b) are preferably formed in this order. In this case, the undercoat layer (a) has the above thickness, and the film thickness (dry film thickness) of the overcoat layer (b) made of an ultraviolet-curable acrylate resin paint is not particularly limited, but is usually 20 to 150 μm.
m, preferably about 60 to 80 μm thick. Such a substrate with a coating film (decorative board) is excellent in warm water resistance, hardness characteristics, meat feeling, stain resistance, etc., and is exposed to harsh conditions, such as a water circulating member such as a bathroom or a kitchen. It can be suitably used as such a member.

<Production method of decorative board> Next, the method of producing the decorative board (inorganic-based decorative board) will be sequentially described. First, the hydroxyl group-containing acrylic polymer in the (undercoat) coating composition (a) will be described.

<Hydroxyl-Containing Acrylic Polymer> Hydroxyl-containing acrylic polymer (acrylic polyol) is an acrylic resin containing one or more hydroxyl groups in one molecule, and (meth) acrylic acid or a derivative thereof is used. It is not particularly limited as long as it is contained as a copolymer component.
(Co) polymer of (meth) acrylic acid and its derivative having a hydroxyl group, (b): (meth) acrylic acid or its derivative having a hydroxyl group, and a carbon-carbon unsaturated double bond (C = C) in the side chain (branch) of an aromatic hydrocarbon (eg, styrene)
Alternatively, a copolymer obtained by copolymerizing a hydrocarbon such as an aliphatic hydrocarbon containing the double bond (eg, an α-olefin having 2 to 20 carbon atoms) may be used. And any of aliphatic and aromatic compounds may be used.

Examples of the hydroxyl group-containing acrylic polymer include resins such as urethane acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester acrylate other than the polyester acrylate, and polyether acrylate.
Preferably, a urethane acrylate resin or an epoxy acrylate resin is used, and particularly preferably, a urethane acrylate resin is used.

Such a hydroxyl group-containing acrylic polymer is, in the presence of a solvent (eg, xylol), compared to an acrylic polymer not containing a hydroxyl group, such as a vinyl propionate polymer or a vinyl chloride polymer. Excellent compatibility with

Hereinafter, particularly preferably used in the present invention,
The urethane acrylate-based hydroxyl-containing acrylic polymer will be described in detail. Used when synthesizing this urethane acrylate-based hydroxyl-containing acrylic polymer,
Derivatives of (meth) acrylic acid include (meth) acrylic esters, (meth) acrylamides, and (meth) acrylamides.
Acrylonitrile and the like can be mentioned.

(Meth) acrylic esters include:
Specifically, for example, 2-hydroxyethyl (meth) acrylate, ethyl-α-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, epoxy acrylate, glycidol di ( Those containing a hydroxyl group, such as (meth) acrylate, pentaerythritol tri (meth) acrylate; and those capable of deriving a hydroxyl group-containing group, such as glycidyl (meth) acrylate containing an epoxy group; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, amyl (meth) acrylate, vinyl (meth) acrylate, β-methallyl (meth) acrylate, cyclohexyl ( Esters having no hydroxyl group such as (meth) acrylate, ethylene glycol diacrylate, glyceryl tri (meth) acrylate, and the like; (meth) acrylic acid; and the like.

Specific examples of (meth) acrylamides include (meth) acrylamide and N-methylolacrylamide. Specific examples of the (meth) acrylonitriles include (meth) acrylonitrile, ethyl cyano (meth) acrylate, and the like.

In the present invention, for example, the above-mentioned monomers are used in an appropriate combination, for example, the above-mentioned hydroxyl-containing (meth) acrylic acid derivative is used in combination with another (meth) acrylic acid and / or a derivative thereof. Can be.

Among these, the combination of monomers includes (a) methyl methacrylate (MMA) / (b)
Butyl acrylate (BA) / (c) 2-hydroxyethyl acrylate (2-HEA), the component weight ratio of which is (a) 6
0 to 70 / (b) 30 to 40 / (c) 5 to 10 [total 100 parts by weight], (a) styrene / (b) methyl methacrylate (MMA) / (c) 2-hydroxyethyl methacrylate (2-HEMA) whose component weight ratio is (a) 20-60
/ (B) 20 to 70 / (c) 10 to 30 [100 parts by weight in total]
And the like are preferably used.

In order to synthesize a hydroxyl group-containing acrylic polymer composed of component units derived from such a monomer, a conventional method may be used.
At a temperature of about 140 ° C., in the presence of a radical initiator such as a peroxide (eg, benzoyl peroxide) or an azobis compound (eg, azobisisobutyronitrile (AIBN)),
These monomers may be (co) polymerized. The hydroxyl group-containing acrylic polymer is considered to contain component units derived from each monomer at a ratio corresponding to the monomer ratio.

These hydroxyl group-containing acrylic polymers are:
One type or a combination of two or more types can be used.
Physical properties such as weight average molecular weight, viscosity, glass transition temperature Tg, etc. of such a hydroxyl group-containing acrylic polymer are as follows: a desired acrylic resin paint is an organic solvent type, an aqueous emulsion type, a non-aqueous emulsion type, a solventless type, and a powder. Etc., or the method of applying the obtained paint is baking coating or curing at room temperature. The weight average molecular weight of the containing acrylic polymer is usually 25,
000 to 50,000, preferably 30,000 to 4
And its glass transition temperature Tg is usually 3
The temperature is about 0 to 90 ° C, preferably about 50 to 80 ° C, and the hydroxyl value is usually 20 to 120 mgKOH / g, preferably 40 to 60 mgKOH / g.

In the aqueous emulsion type paint, the weight average molecular weight of the hydroxyl group-containing acrylic polymer is as follows:
Usually 20,000 to 50,000, preferably 30,0
00 to 40,000, and its glass transition temperature Tg
Is usually about 30 to 90 ° C., preferably about 50 to 80 ° C., and the hydroxyl value is usually 20 to 120 mg KOH / g,
Preferably it is 40-60 mgKOH / g.

The urethane-based hydroxyl-containing acrylic polymer is usually used in combination with a curing agent having two or more isocyanate groups in one molecule (a curing agent for urethane-based resin), and if necessary, a catalyst. May be used in combination with various photopolymerizable monomers, photoinitiators (ultraviolet polymerization initiators), and the like.

As the curing agent for the hydroxyl group-containing acrylic polymer, a polyisocyanate compound is used, which may be either an aromatic or an aliphatic compound. Specifically, tolylene diisocyanate (TDI) , Methylene bisphenyl isocyanate (MDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate (NDI),
Triphenylmethane triisocyanate, tolidine diisocyanate (TODI), xylene diisocyanate, hexamethylene diisocyanate and modified products thereof,
Dicyclohexylmethane diisocyanate (hydrogenated MD
In addition to I), isophorone diisocyanate (IPDI), and the like, those obtained by adding an alcohol to these isocyanates as a base, and dimers and trimers (oligomers) of these isocyanates are exemplified.

These curing agents can be used alone or in combination of two or more. The amount of the OH group in the hydroxyl group-containing acrylic polymer and the amount of the NCO group in the polyisocyanate are set so that these curing agents can react with the hydroxyl group-containing acrylic polymer to form a urethane bond. The curing agent is usually used in an amount such that the molar amount thereof becomes equimolar.
It is used in an amount of about 5 to 50 parts by weight based on parts by weight.

<Vinyl Propionate Polymer> The vinyl propionate polymer in the coating composition (a) is a (co) polymer containing at least a unit derived from a vinyl propionate monomer, If necessary, another monomer may be copolymerized.

Specific examples of such other monomers for copolymerization include vinyl acetate and vinyl chloride. After applying the coating composition (a) containing this vinyl propionate-based polymer to form an undercoat coating film (a),
For example, when applying a UV curable acrylate resin paint (b) as described below as a preferred top coat, it has excellent initial adhesion at the time of coating, and a top coat (b) on the undercoat (a).
Is excellent in warm water resistance (eg, contact with hot water of 80 ° C. for 16 hours) and has good appearance. The undercoating film (a) containing such a vinyl propionate-based polymer also has excellent adhesion to, for example, an overcoating film (b) made of an ultraviolet-curable acrylate resin paint.

The weight average molecular weight of such a vinyl propionate polymer is usually from 10,000 to 25,000,
It is preferably 10,000 to 20,000, and its glass transition temperature Tg is usually 20 to 80 ° C, preferably 3 to 80 ° C.
The temperature is about 0 to 60 ° C., and the vinyl propionate content is usually 20 to 60 mol%, preferably 20 to 40 mol%.

These vinyl propionate polymers are:
One type or a combination of two or more types can be used.
Such a vinyl propionate polymer is usually used in an amount of 10 to 30 parts by weight, preferably 20 to 30 parts by weight, based on 100 parts by weight of the component: hydroxyl group-containing acrylic polymer in the coating composition (undercoat coating composition). Used in an amount of 200 parts by weight.
When the vinyl propionate-based polymer is contained in the coating composition in such an amount, the adhesion of the top coating to the ultraviolet-curable acrylate-based resin coating tends to be improved.

From the viewpoint of stability in the coating composition and workability of coating, the vinyl propionate polymer is usually contained in an amount of 5 parts by weight per 100 parts by weight of solids in the coating composition.
It is desirably contained in an amount of about 30 to 30 parts by weight, preferably about 10 to 20 parts by weight.

<Vinyl chloride-based polymer> The vinyl chloride-based polymer optionally contained in the coating composition (a) (undercoat) used in the present invention includes, in addition to a vinyl chloride homopolymer, vinyl chloride And one or more other vinyl monomers (excluding vinyl propionate).

Examples of such a copolymer of vinyl chloride and another vinyl monomer include a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl propionate copolymer, and a vinyl chloride / alkyl vinyl ether copolymer. Coalescing,
Vinyl chloride-acrylonitrile copolymer, vinyl chloride-
Diethyl maleate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-maleic anhydride copolymer, vinyl chloride-alkyl (meth) acrylate copolymer (alkyl group: about 1 to 5 carbon atoms), chloride Vinyl-styrene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl stearate copolymer, vinyl chloride-maleic acid (or maleate ester) copolymer, vinyl chloride-aliphatic vinyl copolymer And the like.

Further, a graft-modified polyvinyl chloride obtained by graft-polymerizing polyvinyl chloride with another monomer other than vinyl chloride, or a vinyl chloride monomer into another polymer other than polyvinyl chloride Is graft-polymerized.

Examples of the "other monomer" include the above-mentioned monomers for forming a vinyl chloride copolymer, such as alkyl (meth) acrylate (alkyl group: about 1 to 5 carbon atoms), styrene, acrylonitrile, diethyl maleate and the like. Ethates, olefins (eg, ethylene and propylene), maleic anhydride, vinylidene chloride, stearic acid, maleic acid, maleic acid esters, and aliphatic vinyls.

Among these vinyl chloride polymers,
Vinyl chloride-vinyl acetate copolymer or its partial hydrolyzate [Example: vinyl chloride (a) -vinyl acetate (b) -vinyl alcohol (c) copolymer, particularly when the copolymer composition ratio is (a) 80
To 95, (b) 1 to 10, (c) 1 to 10 (however, a total of 100 parts by weight)], the coating composition of the present invention has water resistance,
It is excellent in adhesion and tends to be excellent in adhesion to a UV-curable acrylate resin paint of a top coat.

The weight average molecular weight (Mw) of such a vinyl chloride polymer is usually 5,000 to 50,000, preferably 10,000 to 30,000, particularly preferably 12,000 to 20,000. Desirably. When the weight average molecular weight is in the above range, the compatibility with the hydroxyl group-containing acrylic copolymer tends to be improved.

Among such vinyl chloride polymers,
In a commercially available product, examples of the vinyl chloride / isobutyl vinyl ether copolymer include "Laroflex LR8829", "Laroflex MP25", "Laloflex MP35", and "Laloflex MP45" manufactured by BASF. Vinyl chloride (a) / vinyl acetate
Commercially available (b) / vinyl alcohol (c) copolymers include “DENKA 1000GSK” (Electrochemical Co., Ltd.)
Copolymerization component composition ratio (a) / (b) / (c) = 89/5/6 (total 100 parts by weight), molecular weight (Mw): 15000), vinyl chloride (a) / acetate (b) / As the alcohol (c) copolymer, "VAGD" (manufactured by Union Carbide Co., Ltd., copolymer component composition ratio (a) / (b) / (c) = 90/4/6 (total 10)
0 parts by weight), molecular weight Mw: 15000) and the like.

These vinyl chloride copolymers can be used alone or in combination of two or more. These vinyl chloride-based polymers are usually used in an amount of 20 to 300 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the hydroxyl group-containing acrylic polymer in the coating composition (undercoat coating composition).
It is used in an amount of 0 to 150 parts by weight. When the vinyl chloride-based polymer is contained in the coating composition in such an amount, the coating interval between the top coating and the ultraviolet-curable acrylate-based resin coating tends to be almost free. In addition,
Various stabilizers may be used in combination with such a vinyl chloride polymer. Examples of the PVC stabilizer include “Epiclon 850” (manufactured by Dainippon Ink and Chemicals, Inc.),
Epoxy resin-based stabilizers such as "Epototo YD128" (manufactured by Toto Kasei) and "Epicoat 828" (manufactured by Yuka Shell) are exemplified.

In the present invention, the above-mentioned coating composition (a) is added to the above-mentioned vinyl chloride polymer of the thermoplastic resin together with a vinyl chloride copolymer other than the vinyl chloride copolymer within a range not inconsistent with the object of the present invention. "Other thermoplastic resin" may be contained.

Specific examples of the thermoplastic resin (rubber) other than the vinyl chloride-based polymer include chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; styrene-based resins; Resins; aliphatic petroleum resins; urea aldehyde condensation resins; ketone resins; chromamandene resins; pentadiene polymers.

These thermoplastic resins (rubbers) can be used alone or in combination of two or more. <Optional components> The coating composition (a) used in the present invention includes:
In addition to the above, various components that are blended in ordinary paints may be included.

Such optional components include pigments (colorants), activators, fillers, etc., as well as solvents, modifiers,
Examples include a non-crosslinkable polymer and a curing modifier. The optional components such as a pigment (colorant), an activator, and a filler can take any shape such as a powder, a lump, a flake, and a fiber according to the use, function, and required physical properties.

Examples of pigments (including coloring agents) include inorganic carbon black, titanium dioxide, iron oxide, iron hydroxide,
Bengala, chromium oxide, graphite, ultramarine, various alloys, white carbon, alumina, fused alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide, clays; organic insoluble azo pigments, soluble azo pigments, polycondensates Cyclic pigments, quinacridone pigments, isoindolinone pigments, cyanine blue, cyanine green and the like.

As the activator, specifically, for example, a boric acid-containing compound, a lead-containing compound, a chromic acid-containing compound,
Phosphoric acid-containing compounds and the like. When such an activator is previously incorporated into the coating composition of the present invention, when the object to be coated is a metal such as iron, the coating film of the coating composition and the object to be coated There is a tendency that adhesion is improved and anticorrosion is improved.

Specific examples of the filler include metals and alloys such as stainless steel, silicon, zinc, aluminum and iron. These may be in the form of paste, flake or powder.

In addition, glass, porcelain, diamond, silicon oxide (silica sand, silica stone, silica, etc.), magnesium, calcium carbonate, zircon sand, various clays, calcined clay (eg, bauxite, montmorillonite, kaolin, etc.), gypsum , Calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate, magnesium silicate, barium silicate, barium carbonate, barium hydroxide, aluminum silicate, talc,
Powders such as mica, fly ash, and soda feldspar are mentioned.

In the present invention, these components can be used alone or in combination of two or more. Among these optional components, for example, pigments (colorants), activators, and fillers are usually 2, 2 with respect to 100 parts by weight of the components in the coating composition: hydroxyl group-containing acrylic polymer.
It is used in an amount of up to 2,000 parts by weight, preferably up to 1,000 parts by weight.

The solvent is substantially inert with respect to each component in the coating composition (a), and as long as the components such as a polymer in the composition can be dissolved or dispersed, the coating workability is improved. From the viewpoint of the above, conventionally known ones can be widely used.

Specific examples of such a solvent include hydrocarbon solvents such as toluene, xylene, pentane, hexane and heptane; acetone, methyl ethyl ketone, and the like.
Ketones such as methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate; dioxane;
Alcohols such as ethanol, butanol, and isopropyl alcohol; and the like. These solvents can be used alone or in combination of two or more depending on the curing method or the like.

In consideration of the dissolution / dispersibility of each component and the coating workability of the coating composition, these solvents are usually used in an amount of 100 parts by weight of the non-volatile components in the coating composition (a). 10 to 2000 parts by weight, preferably 20 to 10 parts
It is used in an amount of 00 parts by weight.

As a modifying agent, a leveling agent, a dispersant,
Conventionally known ones such as an antifoaming agent, a viscosity-imparting agent, and a storage stabilizer, which are usually blended in a paint, may be used. Examples of the non-crosslinkable polymer include a solvent-type or dispersion-type organic polymer, which can form a solidified body by volatilization of the coexisting solvent at ordinary temperature or under heating. Are, for example, cellulose resins (eg, nitrocellulose, acetylcellulose, acetylbutylcellulose, ethylcellulose, etc.), urethane resin, vinyl chloride organosol dispersion, fluorine resin, alkyd resin, vinyl acetate resin, styrene resin.
Butadiene-based resin, silicone-based resin, colloidal silica or alumina dispersion, or the like is used.

The non-crosslinkable polymer is used in an amount of, for example, 20 parts by weight or less based on 100 parts by weight of the hydroxyl group-containing acrylic polymer. <Method of applying (undercoat) coating composition to substrate> The (undercoat) coating composition (a) used in the present invention is applied to the surface of various substrates (substrate) by a conventionally known method. Painted.

The coating composition (a) is usually used as a solvent type. For example, a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer (and optionally contained) in the above-mentioned coating composition (a) are used. A resin component containing a vinyl chloride polymer) and a curing agent for urethane resin (eg, TDI, I
It is stored and handled in a two-part system with a curing agent-based component including PDI, HDI, etc., and a catalyst (eg, dibutyltin dilaurate (DBTDL), tin octylate, etc.). The components may be mixed, applied to the surface of the substrate (substrate), dried and cured.

More specifically, the object to be coated is not particularly limited, and as described above, an inorganic substrate (eg, slate)
And the like. The coating method is not particularly limited, and a conventionally known method can be employed. For example, a roll coater, a flow coater, an airless spray, an air spray, a brush coating, a trowel coating, a roller coating, a dipping, a lifting, a flow coating, and a laying For example, a conventional method may be used.

Prior to the above coating, if necessary,
Cleans rust, oil, water, dust, etc.
Remove, sealer, binder,
A primer or the like may be applied. Further, the above-mentioned sealer or the like may be appropriately diluted with a thinner or the like before use.

The amount of the coating composition (a) to be applied depends on the type of the object to be coated (substrate), the type of the top coat to be overcoated,
Although it differs depending on the combination, etc., and is not determined unequivocally, when applied to members exposed to harsh conditions, such as interior materials such as bathrooms and kitchens, water supply members, etc., the coating composition of the present invention (undercoating) Coating composition) is, for example, 120 to 200 g / m
The amount of ² is about 100 to 160 μm thick, and the dry film thickness is about 30 to 60 μm as described above.

In addition, this coating composition (a) and the following top coating (example: UV-curable acrylate resin coating) (b)
Is not particularly limited and can be appropriately set according to the paint concentration, the required film thickness, etc., and may be once or plural times, respectively.

The method of drying and curing the coating composition (a) differs depending on the type of the curing agent in the coating composition (a), and may be, for example, baking (for example, 200 to 230 ° C.).
For 2 to 5 minutes), drying by heating (example: 100 to 150 ° C)
For 10 to 15 minutes), drying at room temperature, and photo-curing (UV irradiation).

The substrate (decorative board) with the coating film (a) made of this coating composition, which is obtained by drying and curing as described above, can be used, for example, in a hot water drainage member such as a bathroom or kitchen. Swelling, peeling, and the like are unlikely to occur even at locations and members exposed to severe conditions such as contact with the surface. When a top coat (b) made of the following UV-curable acrylate resin paint is formed on the coat (a) made of this coating composition,
A decorative plate having excellent adhesion between (a) and the layer (b) is obtained.

Next, in a preferred embodiment of the present invention, the overcoat layer (b) applied and formed on the undercoat layer (a) composed of the coating composition will be described. <Overcoat> In the present invention, the above-mentioned coating composition (a) is used as an undercoat, and various overcoats are coated on a coating film (undercoat (a)) composed of the undercoat (a). (b) may be painted.

Examples of such a top coat (a) include oily (alkyd), phthalic acid resin, chlorinated polyolefin (chlorinated rubber), vinyl, acrylic, epoxy, urethane, and silicone alkyd. Acrylic silicone-based, fluororesin-based topcoats and the like can be mentioned, among which acrylic-based ones are preferred, and a topcoat film (b) composed of an ultraviolet-curable acrylate-based resin paint as described below is particularly preferred for the undercoat. This is desirable because of its excellent adhesion to the coating film (a).

When an ultraviolet-curable acrylate-based resin paint is applied as the top coat, for example, the ultraviolet-curable acrylate-based resin paint (b) is, for example, 80 to 1%.
It is applied in an amount of 00 g / m ^{2 to} a thickness of about 80 to 100 μm, and its dried (cured) film thickness is 60 to 8 as described above.
It is about 0 μm.

[Ultraviolet curable acrylate resin paint
(b)] UV curable acrylate resin paint (b), which is a top coat preferably used in the present invention, includes (a) an acrylate UV curable resin, and (b) polyisocyanate,
And (c) an ultraviolet polymerization initiator.

The acrylate-based UV-curable resin (a) may be either an aliphatic-based or aromatic-based resin, such as a urethane acrylate-based UV-curable resin, an epoxy acrylate-based UV-curable resin, or a polyester acrylate-based UV-curable resin. Mold resins, unsaturated polyester-based UV-curable resins other than polyester acrylate-based UV-curable resins, polyether acrylate-based UV-curable resins, and the like. Urethane acrylate-based UV-curable resins and polyester acrylate-based UV-curable resins include It is preferably used.

These acrylate UV-curable resins
(A) usually contains a photopolymerizable monomer in addition to the photopolymerizable oligomer that is the base resin of each resin. In a photopolymerizable oligomer urethane acrylate-based ultraviolet curable resin, urethane acrylate is used as a main polymer (base resin) of a photopolymerizable oligomer. The urethane acrylate is obtained, for example, by reacting the diisocyanates (polyisocyanate) with the polyols and the hydroxy acrylates, and has an acryloyl group (CH ₂ ＣＨCHCO—) as a functional group in the molecule and a urethane bond (−). It is a prepolymer (oligomer) having NH.COO-).

Specific examples of polyols include poly (propylene oxide) diol, poly (propylene oxide) triol, poly (tetramethylene oxide) diol, and ethoxylated bisphenol A.

In an epoxy acrylate-based UV-curable paint, epoxy acrylate is used as a photopolymerizable oligomer. This epoxy acrylate is synthesized by reacting an epoxy compound such as epichlorohydrin with acrylic acid or methacrylic acid.

As the epoxy acrylate, specifically, bisphenol A type epoxy acrylate synthesized by reaction of bisphenol A with epichlorohydrin and acrylic acid, bisphenol S type synthesized by reaction of bisphenol S with epichlorohydrin and acrylic acid Epoxy acrylate, bisphenol F epoxy acrylate synthesized by reaction of bisphenol F, epichlorohydrin and acrylic acid, phenol novolak epoxy acrylate synthesized by reaction of phenol novolak, epichlorohydrin and acrylic acid, and the like are exemplified.

Further, in the polyester acrylate ultraviolet curing resin, polyester acrylate is used as a photopolymerizable oligomer of the base resin. This polyester acrylate is obtained by condensing acrylic acid with a hydroxyl group remaining in the skeleton of a polyester synthesized by reacting a diol or polyol with a dibasic acid.

As the polyester acrylate, specifically, an acrylate synthesized by a reaction of phthalic anhydride, propylene oxide and acrylic acid, or a synthetic reaction of adipic acid, 1,6-hexanediol and acrylic acid. Acrylates, acrylates synthesized by the reaction of trimellitic acid, diethylene glycol and acrylic acid, and the like are included.

The photopolymerizable oligomer contained in the unsaturated polyester UV-curable resin other than the above-mentioned polyester acrylate UV-curable resin includes, specifically, 1,2-propylene glycol and anhydrous phthalate. Unsaturated polyester consisting of acid and maleic anhydride; trimethylolpropane diallyl ether (TMP
DA), trimethylolpropane triallyl ether (TMPTAE), an unsaturated polyester in which an allyl group-containing compound such as triallyl isocyanate or diallyl phthalate is blended with styrene.

The photopolymerizable oligomer was added in an amount of 1 part by weight to 100 parts by weight of the entire UV-curable acrylate resin paint.
It is used in an amount of 0 to 95 parts by weight, preferably 40 to 90 parts by weight.

Examples of the photopolymerizable monomer (acrylic monomer) include 2-ethylhexyl acrylate, phenoxyethyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, 2-hydroxypropyl acrylate, and methyltriglycol. Acrylate,
Monofunctional monomers such as isodecyl acrylate; 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate,
Bifunctional monomers such as diethylene glycol diacrylate, triethylene glycol diacrylate, and tetraethylene glycol diacrylate; and polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. These photopolymerizable monomers can be used alone or in combination of two or more.

The photopolymerizable monomer is used in an amount of 0 to 100 parts by weight of the whole UV-curable acrylate resin paint.
It is used in an amount of 70 parts by weight, preferably 0 to 50 parts by weight.

Polyisocyanate (b) (Active) The polyisocyanate (b) has, for example, a function of curing a resin. Examples of such a polyisocyanate include those described above.

The polyisocyanate (b) is used in an amount of 1 to 30 parts by weight, preferably 3 to 10 parts by weight, based on 100 parts by weight of the whole UV-curable acrylate resin coating.

The ultraviolet polymerization initiator (c) The ultraviolet polymerization initiator (c) (photoinitiator) is not particularly limited, and conventionally known ones can be used. Specifically, for example, benzoin, benzoin Ethyl ether,
Benzoin isopropyl ether, benzophenone, benzyl dimethyl ketal and the like can be mentioned. These ultraviolet polymerization initiators can be used alone or in combination.

The ultraviolet polymerization initiator (c) is contained in 100 parts by weight of the total amount of the ultraviolet curable acrylate resin paint.
It is used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight.

In addition to the above-mentioned components, these overcoat paint compositions include, in addition to the above-mentioned oligomers and various monomers copolymerizable with the monomers (for example, acrylic monomers and vinyl monomers other than the above-mentioned ones), the above-mentioned well-known materials which have been known in the art. Such additives (eg, extender, solvent, leveling agent, defoaming agent, water absorbing agent, etc.) may be blended.

In addition, these coating compositions for overcoating include conventionally known polyester acrylate UV-curable resins, unsaturated polyester UV-curable resins other than polyester acrylate UV-curable resins, and polyether acrylate UV-curable resins. [Example: Epoxy acrylate UV curable resin 1]
Total amount of resin such as urethane acrylate-based ultraviolet curable resin is 0 to 99 parts by weight with respect to 00 parts by weight].

The UV-curable acrylate resin paint for top coating is prepared by using the above-mentioned photopolymerizable oligomer, photopolymerizable monomer, ultraviolet polymerization initiator (photoinitiator), water absorbing agent,
It can be obtained by mixing an extender, a solvent, and the like.

For example, when the ultraviolet-curable acrylate-based resin coating material is a polyurethane acrylate-based coating material, such a coating composition is packaged in a polyisocyanate as a curing agent and a component such as a polyol as a main component, and is mixed with two components. It is stored and handled as a mold, but at the time of painting, these components for the paint are blended and used in a fixed ratio. As a method of coating and curing, it is only necessary to apply UV in the same manner as the undercoat paint composition (a) and then to cure it by UV.

As described above, the undercoat layer composed of the undercoat paint
On top of (a), applying and curing the above UV-curable acrylate resin paint to produce a decorative board, particularly an inorganic decorative board,
These paints, especially UV-curable acrylate resin paints, contain only a small amount of organic solvents compared to conventional paints, so they do not pollute the environment even if the organic solvents used during the production of decorative boards diffuse around. Less likely to cause. Moreover, as described above, the decorative board obtained by sequentially applying the base coat (a) and the top coat (b) on the surface of the base material, particularly the inorganic base material, has a warm water resistance, a hardness characteristic, a solid feeling, a stain resistance. Excellent in properties and the like. Therefore, this decorative board can be suitably used as a water supply member for kitchens, washrooms, bathrooms, and the like.

[0093]

The decorative board according to the present invention is excellent in warm water resistance, hardness properties, feeling of holding, stain resistance and the like. Further, the decorative sheet according to the present invention comprises a sealer and an undercoat coating film (undercoat layer).
(a)), excellent adhesion between undercoat and overcoat (especially UV-curable acrylate resin coating, overcoat (b)) etc., for example, materials for water-running parts in bathrooms, kitchens, etc. Even if applied to places exposed to severe conditions, the decorative board does not swell or peel off, and can be suitably used for these parts.

At the time of manufacturing the decorative board according to the present invention, particularly an inorganic decorative board, since the undercoat composition containing a vinyl propionate polymer is used, this undercoat composition is applied. For example, when a UV-curable acrylate resin paint is applied as a top coat after coating, the application time (coating interval) is almost free, and the coating interval can be easily set arbitrarily and the coating workability is excellent. Moreover, in this decorative board, the adhesion between the undercoating film (a) made of the undercoating composition and the topcoating film (b) made of the UV-curable acrylate resin paint is good.

[0095]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the following examples, comparative examples, and the like,
Means "parts by weight". In addition, the amount of each component in the table is
All parts are indicated by "parts by weight" unless otherwise specified. ★ Sealer: 8 parts of HDI-based isocyanate [Chalk Paint Co., Ltd., alkali sealer NY-2] and 12 parts of urethane resin solvent [China Paint Co., Ltd., urethane thinner A] 12 parts by air disperser. A sealer was prepared by stirring and mixing for minutes. ★ Undercoat paint composition: The total amount of the composition shown in Table 2 below or the composition shown in Table 2 except that one part of the organic solvent was removed was blended in a tank, and the mixture was uniformly stirred with a disper.

Next, using a sand mill (glass beads SG), while keeping the coating temperature below 40 ° C.,
The mixture was kneaded and dispersed so as to have a particle size of 0 μm or less to prepare a coating composition for undercoat. ★ Coating composition for top coat

[0098]

[Table 1]

The above components having the above composition ratios are blended in a tank,
While maintaining the liquid temperature at 40 ° C. or less, the mixture was uniformly kneaded and dispersed with a disper to prepare a top coating composition. [Preparation of test plate] <Sealer> Commercially available slate plate [30 × 30 × 0.5c]
m], a sealer of the above composition is applied to about 30 g / m ²
And dried at a temperature of 80 ° C. for 10 minutes to obtain a dry film thickness of 3 μm.

<Undercoating> Next, a curing agent [HDI polyisocyanate, trade name: 73-] was applied to the surface of the sealer-coated slate plate with respect to 100 parts by weight of the undercoating coating composition having the above composition. D, China Paint Co., Ltd.
6.25 parts by weight, uniformly agitated with a spoon, brush-coated at an amount of about 130 g / m ² , kept at a temperature of 60 ° C. for 2 minutes, and then attached at a position 10 cm away from the slate plate. When the slate plate was heated at a plate surface temperature of 128 ° C. for 2 minutes using the infrared lamp, the dry film thickness became 50 μm (undercoat layer). <Overcoating> Then, the surface of the undercoated slate plate was coated with the above-mentioned overcoating coating composition for about 9 hours.
Brush-painted in an amount of 0 g / m ² , kept at a temperature of 80 ° C. for 3 minutes, and irradiated with UV (IST: 80 (W / cm) × 5 (m / min)
× 1 (lamp)), the dry film thickness was 75 μm (overcoat layer). [Adhesion test] Evaluation method: Cross-cut tape method (JIS 5400.8.
(Based on 5.2) and evaluated by the number (x) of remaining squares in 25 pieces of 25 mm cross-cut cellophane tape (x / 2).
5). [Appearance evaluation criteria of hot water resistance test] 5: No abnormality 4: Swelling of φ1 mm or less is observed at 5% or less of test plate area 3: Swelling of φ1 mm or less exceeds 5% of test plate area ~
10% or less recognized 2: Swelling of 1 to 5 mm in diameter is 20% or less of test plate area 1: 1 to 5 mm of swelling is recognized in 20% or more of test plate area [Comprehensive evaluation criteria] 5: Practical as a water circulating member 4: A material that withstands practicality as a water circulating member 3: A material with poor practicability as a water circulating member 2: A material that does not withstand practicality as a water circulating member 1: As a water circulating member Non-practical [Evaluation of secondary adhesion (undercoat + overcoat)] A test plate was immersed in warm water at 80 ° C for 1 day, and the degree of blistering and peeling was determined by ASTM.
The adhesiveness was visually evaluated according to D610, and the adhesion was evaluated based on the cross-cut tape method (based on JIS K5400, 8.5.2.). x) (x / 25).

Table 2 shows the evaluation results. The composition and physical properties of the components used in Examples and Comparative Examples are shown below. (1) Solvent: (MIBK: methyl isobutyl ketone), (2) Vinyl chloride polymer: Trade name (Denka 1000GS
K), copolymerization components and composition ratio (vinyl chloride / vinyl acetate / vinyl alcohol) = 89/5/6, molecular weight (Mw:
15000, manufactured by Denki Kagaku Kogyo KK). (3) Vinyl propionate-based polymer: trade name "Ryuron QS-430", manufactured by Tosoh Chemical Co., Ltd., copolymerization components and composition ratio (vinyl perfluoronate / vinyl chloride) = 30/70
(Total 100 parts by weight), molecular weight (Mw: 15,500
0), nonvolatile content NV100%. (4) Hydroxyl-free acrylic polymer: trade name "ACP-20"
1 ", manufactured by Ohtake Chemical Co., Ltd., copolymerized components and composition ratio (MM
(A / BMA) = 60/40 (total 100 parts by weight), molecular weight Mw: 4,000 to 10,000, nonvolatile content NV.4
0. (5) Antifoaming agent: trade name (Floren AC-300), manufactured by Kyoeisha Chemical Co., Ltd., vinyl polymer. (6) Filler (talc): Trade name: Micro Ace L-1, manufactured by Nippon Talc Co., Ltd., average particle size 2 μm. (7) Extender (Kaolin): Trade name: HA Kaolin, manufactured by Fuji Talc. (8) Hydroxyl-containing acrylic polymer: Trade name: Hitaloid 3001X, manufactured by Hitachi Chemical Co., Ltd., M
MA-based copolymer, molecular weight Mw: 42,000, nonvolatile content (NV.): 50%. (9) Titanium white (for ultra-weatherproof): filler, manufactured by DuPont, USA. (10) Colorant: The following (a) to (c) are used.

(A) Trade name: "EP Coat (tone) Oxide Yellow XLO", manufactured by China Paint Co., Ltd. (B) Trade name: “EP coat (tone) black A”, manufactured by China Paint Co., Ltd.

(C) Trade name: “EP coat (tone) white R”,
Made by China Paint Co., Ltd. (11) HDI-based polyisocyanate: Trade name: “Curing Agent 73-D”, manufactured by China Paint Co., Ltd.

Component [Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.) 35 parts, xylene: 65 parts]

[0105]

[Table 2]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B05D 7/24 302 B05D 7/24 302K B32B 9/00 B32B 9/00 A 27/30 27/30 AZ 101 101

Claims (6)

[Claims] 1. A decorative board comprising a coating material comprising a coating composition containing a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer on a surface of a substrate. 2. An undercoat film (a) comprising a coating composition containing a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer on the surface of a substrate, and a top coat comprising an ultraviolet-curable acrylate resin paint. Paint film
(b), and veneers are formed in this order. 3. The decorative plate according to claim 1, wherein the coating composition for an undercoat film further contains a vinyl chloride polymer. 4. The substrate according to claim 1, wherein said base material is an inorganic material.
A decorative plate according to any one of the above. 5. A coating composition containing a hydroxyl group-containing acrylic polymer and a vinyl propionate polymer is applied to the surface of a substrate, and an ultraviolet-curable acrylate resin paint is applied on the obtained coating film. A method for producing a decorative board, comprising applying and curing. 6. The method according to claim 5, wherein the substrate is an inorganic material.