JPH11179837A - Coated molded plate and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve abrasion resistance, weatherability, freeze-thawing resistance, and stain-resistance of a coated molded plate by a method wherein an inner layer coming in contact with a most outer layer is a cured material layer containing activation energy beam curing multifunctional compound, and the most outer layer comprises a layer of curing coated composition capable of forming silica. SOLUTION: A coating cured material layer of an inorganic material plate comprises two layers or more of an inner layer coming in contact with a most outer layer and the most outer layer. A coating composition coming in contact with the most outer layer contains a multifunctional compound having two or more activation energy beam curing polymeric functional groups. As the compound, for example a polyester of a polyhydric alcohol or the like and (meth)acrylic acid is exemplified, and especially, (meth)acryloyl group-containing compound having an urethane bond and (meth)acrylate ester compound having no urethane bond and especially preferable. As the curable coating composition capable of forming silica in the most outer layer, there are tetrafunctional hydrolyzable silane compound, hydrolytic condensate thereof, polysilazane, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for forming a layer of a cured product derived from an active energy ray (especially ultraviolet) curable coating composition on an inorganic plate as an inner layer and silica as an outermost layer in contact with the inner layer. TECHNICAL FIELD The present invention relates to a coated molded plate having a silica layer derived from a coating composition obtained and having excellent abrasion resistance, weather resistance, and the like, and a method for producing the coated molded plate.

[0002]

2. Description of the Related Art In recent years, as a building material such as an outer wall material or a roof material of a house, an inorganic plate excellent in design, heat insulation and durability has been frequently used. This inorganic plate is provided by mixing a hydraulic inorganic material such as cement with asbestos, wood chips, wood wool, pulp or the like as a reinforcing material. Generally, a synthetic resin paint is applied to the surface of such an inorganic plate in order to impart durability and design.

However, since synthetic resin paints have low abrasion resistance and easily generate pinholes, the internal base material is degraded by the ingress of moisture or carbon dioxide from the outside, and effluent by the precipitation of calcium carbonate from the inside. It is liable to cause the redness phenomenon and frost damage.

If a thick paint film is applied to form a thick paint film, the occurrence of pinholes can be prevented and the durability can be improved. However, a large amount of paint is required and the cost is increased. In the film, the sharpness of the design is impaired, and the blocking phenomenon when stacked is likely to occur. Also,
In recent years, buildings have been required to have easy cleaning properties. However, conventional coating films are liable to be worn during cleaning, and there is also a problem that durability and design are reduced.

In recent years, there has been proposed a method for improving abrasion resistance and weather resistance by applying a silica-based inorganic coating film to the outermost layer. However, the conventional inorganic coating film has a disadvantage that a long-time heat treatment is required at a high temperature.

[0006]

The present invention seeks to overcome the aforementioned disadvantages. That is, an object of the present invention is to provide a coated molded plate for building materials and the like which is extremely excellent in abrasion resistance, weather resistance, freeze-thaw resistance, stain resistance, and the like, and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a coated molded plate comprising an inorganic plate and at least two hardened material layers provided on at least a part of the surface of the inorganic plate. The inner layer in contact with the outermost layer has the following coating composition (A)
Wherein the outermost layer is a layer of a cured product of the following coating composition (B), and a method for producing the same. Coating composition (A): An active energy ray-curable coating composition containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups. Coating composition (B): a curable coating composition capable of forming silica.

In the present invention, the cured product layer is composed of two or more layers, and when the coating composition (A) is in direct contact with the inorganic plate, the coating composition (A) in contact with the inorganic plate has a low viscosity before curing. And then enter the pores on the surface of the inorganic plate, and then cure to serve as a filler. For this reason, the cured product layer adheres well to the inorganic plate, and the efflorescence phenomenon from the inside can be prevented to some extent. The layers of these cured products are usually transparent.

At the same time, a layer of silica derived from the coating composition (B) is formed on a hardened layer of a certain degree provided by the coating composition (A), so that extremely excellent abrasion resistance and stain resistance are obtained. Express. In addition, this silica layer blocks the efflorescence phenomenon from the inside and the ingress of moisture and carbon dioxide from the outside, preventing carbonation of the inorganic plate, dimensional changes due to moisture transfer and frost damage, and extremely high durability. It is thought that.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the inorganic plate in the present invention, there is a plate made of an inorganic material such as cement, slag, gypsum and calcium silicate. In particular, cement, inorganic hydraulic substances such as slag, silica sand, pearlite,
Aggregates such as zeolite and vermiculite, asbestos, wood chips,
It is preferable to mix a fiber reinforcing material such as wood wool and pulp and the like, produce it by a dry method, a semi-dry method, a wet method, or the like, and serve as a building plate.

The cured product layer in the present invention comprises at least two layers, an inner layer in contact with the outermost layer and an outermost layer. A third layer made of a synthetic resin or the like may exist between the inorganic plate and the cured product layer. For example, a coating composition (A),
A layer formed from a coating agent other than (B), an adhesive layer or a filler material layer may be present. The cured product layer in the present invention usually comprises two layers, an inner layer and an outermost layer. The inner layer may be composed of two or more different types of cured product layers formed from the coating composition (A).

The coating composition (A) is a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups (hereinafter referred to as “two or more active energy ray-curable polymerizable functional groups”). Having a polyfunctional compound (a) "also referred to as" compound (a) "and" an active energy ray-curable polymerizable functional group "simply referred to as" polymerizable functional group ").

In the following description, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. (Meth) acryloyloxy group, (meth)
The same applies to acrylic acid and (meth) acrylate.

Examples of the polymerizable functional group in the compound (a) include an α, β-unsaturated group such as a (meth) acryloyl group, a vinyl group and an allyl group, and a group having the same.
A (meth) acryloyl group or a (meth) acryloyloxy group is preferred. An acryloyl group or an acryloyloxy group which is easily polymerized by ultraviolet rays is particularly preferred.

The compound (a) may be a compound having two or more kinds of polymerizable functional groups in total, or a compound having two or more same polymerizable functional groups in total. The number of polymerizable functional groups in the compound (a) may be two or more,
Although the upper limit is not particularly limited, usually 2 to 50 pieces are suitable, and 2 to 30 pieces are particularly preferable.

As the compound (a), a compound having two or more (meth) acryloyl groups is preferable, and a compound having two or more (meth) acryloyloxy groups is particularly preferable. Compounds having two or more acryloyloxy groups are more preferable because they are easily polymerized by ultraviolet rays.
Examples of the compound having two or more (meth) acryloyloxy groups include a polyester of a compound having two or more hydroxyl groups (eg, a polyhydric alcohol) and (meth) acrylic acid.

The coating composition (A) may contain two or more compounds (a). Compound (a)
In addition, a monofunctional compound having one polymerizable functional group may be included.

When the coating composition (A) contains two or more compounds (a), these compounds (a)
Compounds having the same polymerizable functional group or compounds having different polymerizable functional groups may be used. For example, a combination of different compounds, each of which is the following acrylic urethane, or a combination of one of which is acrylic urethane and the other is an acrylate compound having no urethane bond may be used.

As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. When the coating composition (A) contains the monofunctional compound, the ratio of the monofunctional compound to the total of the compound (a) and the monofunctional compound is preferably 0 to 60% by weight, and 1 to 30% by weight. % By weight is particularly preferred. If the proportion of the monofunctional compound is too large, the hardness of the cured coating film may be reduced and the abrasion resistance may be insufficient.

The compound (a) may be a compound having various functional groups or bonds other than two or more polymerizable functional groups. For example, hydroxyl group, carboxyl group, halogen atom, urethane bond, ether bond, ester bond,
It may have a thioether bond, an amide bond and the like. Of these, a (meth) acryloyl group-containing compound having a urethane bond (so-called acryl urethane) and a (meth) acrylate compound having no urethane bond are particularly preferable. Hereinafter, these two types of polyfunctional compounds will be described.

Examples of the (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane) include the following. (1) A reaction product of a compound (X1) having a (meth) acryloyl group and a hydroxyl group and a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate). (2) A reaction product of the compound (X1), the compound (X2) having two or more hydroxyl groups, and a polyisocyanate. (3) A reaction product of the compound (X3) having a (meth) acryloyl group and an isocyanate group with the compound (X2).

In these reaction products, it is preferable that no isocyanate group is present, but a hydroxyl group may be present. Therefore, in the production of these reaction products, it is preferable that the total number of moles of hydroxyl groups of all reaction raw materials is equal to or larger than the total number of moles of isocyanate groups.

The compound (X1) may be a compound having one (meth) acryloyl group and one hydroxyl group,
It may be a compound having two or more (meth) acryloyl groups and one hydroxyl group, a compound having one (meth) acryloyl group and two or more hydroxyl groups, or two or more (meth) acryloyl groups and two hydroxyl groups. A compound having the above may be used.

As a specific example, for example, 2-
Examples include hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, and pentaerythritol di (meth) acrylate. These are monoesters of a compound having two or more hydroxyl groups and (meth) acrylic acid or polyesters having one or more hydroxyl groups.

The compound (X1) may be a ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid. The reaction between the epoxy group and the (meth) acrylic acid causes the ring opening of the epoxy group to form an ester bond and a hydroxyl group to form a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the epoxy group of a compound having one or more epoxy groups may be opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

As the compound having one or more epoxy groups, a polyepoxide called an epoxy resin is preferable. As the polyepoxide, a compound having two or more glycidyl groups such as a polyhydric phenol-polyglycidyl ether (for example, bisphenol A-diglycidyl ether) or an alicyclic epoxy compound is preferable. Further, a reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group can also be used as the compound (X1). Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate.

The polyisocyanate may be an ordinary monomeric polyisocyanate, a multimer or modified polyisocyanate, or a prepolymer compound such as an isocyanate group-containing urethane prepolymer.

Examples of the polyisocyanate multimer include a trimer (isocyanurate modified product), a dimer, and a carbodiimide modified product. Examples of the modified polyisocyanate include urethane modified, buret modified, allohanate modified, and urea modified products obtained by modification with a polyhydric alcohol such as trimethylolpropane. Examples of prepolymers include isocyanate group-containing urethane prepolymers obtained by reacting polyols such as polyether polyols and polyester polyols described below with polyisocyanates. These polyisocyanates can be used in combination of two or more.

Specific examples of the monomeric polyisocyanate include the following polyisocyanates (the names in [] are abbreviated). 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, methylene bis (4-phenyl isocyanate) [MDI], hexamethylene diisocyanate, isophorone diisocyanate, transcyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI], Hydrogenated XD
I, hydrogenated MDI.

As the polyisocyanate, a non-yellowing polyisocyanate (polyisocyanate having no isocyanate group directly bonded to an aromatic nucleus) is particularly preferable. Specific examples include aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and aromatic polyisocyanates such as xylylene diisocyanate. As described above, polymers and modified products of these polyisocyanates are also preferable.

Examples of the compound (X2) include polyhydric alcohols and polyols having a higher molecular weight than polyhydric alcohols. As the polyhydric alcohol, a polyhydric alcohol having 2 to 20 hydroxyl groups is preferable, and a polyhydric alcohol having 2 to 15 hydroxyl groups is particularly preferable. The polyhydric alcohol may be an aliphatic polyhydric alcohol, an alicyclic polyhydric alcohol or a polyhydric alcohol having an aromatic nucleus. Examples of the polyhydric alcohol having an aromatic nucleus include an alkylene oxide adduct of a polyhydric phenol and a ring-opened product of a polyepoxide having an aromatic nucleus such as polyhydric phenol-polyglycidyl ether.

The high molecular weight polyol includes polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol and the like. Further, a hydroxyl group-containing vinyl polymer can also be used as the polyol. These polyhydric alcohols and polyols can be used in combination of two or more.

Specific examples of the polyhydric alcohol include the following polyhydric alcohols. ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,
6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, ring-opened product of bisphenol A-diglycidyl ether, and ring-opened product of vinylcyclohexene dioxide.

Specific examples of the polyol include the following polyols. Polyether polyols such as polyethylene glycol, polypropylene glycol, bisphenol A-alkylene oxide adduct, and polytetramethylene glycol. A polyester polyol obtained by ring-opening polymerization of a cyclic ester such as poly-ε-caprolactone polyol. Adipic acid, sebacic acid, phthalic acid,
A polyester polyol obtained by reacting a polybasic acid such as maleic acid, fumaric acid, azelaic acid, glutaric acid and the above polyhydric alcohol. A polycarbonate diol obtained by reacting 1,6-hexanediol with phosgene.

Examples of the hydroxyl group-containing vinyl polymer include a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether and hydroxyalkyl (meth) acrylate and a hydroxyl group-free monomer such as olefin. . Compound (X3)
Examples thereof include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

As the (meth) acrylic acid ester compound having no urethane bond as the compound (a), a polyester of a compound having two or more hydroxyl groups and a polyester of (meth) acrylic acid, similar to the compound (X2), can be used. preferable. As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable. Further, a (meth) acrylate compound which is a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid is also preferable.

As a compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin. For example, glycidyl ether type polyepoxide,
A commercially available epoxy resin such as an alicyclic polyepoxide can be used.

Specific examples of the polyfunctional compound containing no urethane bond include the following compounds.
(Meth) acrylates of the following aliphatic polyhydric alcohols.
1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, triglycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

The following (meth) acrylates of the following polyhydric alcohols and polyphenols having an aromatic nucleus or a triazine ring. Tris (2- (meth) acryloyloxyethyl)
Isocyanurate, bis (2- (meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) bisphenol A, Bis (2- (meth) acryloyloxyethyl) bisphenol S, bis (2- (meth) acryloyloxyethyl) bisphenol F, tris (2- (meth) acryloyloxyethyl) isocyanurate, bisphenol A dimethacrylate.

The following (meth) acrylates of hydroxyl-containing compounds-alkylene oxide adducts, (meth) acrylates of hydroxyl-containing compounds-caprolactone adducts, and (meth) acrylates of polyoxyalkylene polyols.
Here, EO represents ethylene oxide, and PO represents propylene oxide. Trimethylolpropane-EO adduct tri (meth) acrylate, trimethylolpropane-
PO adduct tri (meth) acrylate, dipentaerythritol-caprolactone adduct hexa (meth) acrylate, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct tri (meth) acrylate, tris (2-hydroxypropyl) ) Tri (meth) acrylate of isocyanurate-caprolactone adduct.

Since the cured product of the coating composition (A) can exhibit sufficient abrasion resistance, the compound (a) is a multifunctional compound having at least a part (preferably 30% by weight or more) of trifunctional or more. It is preferable that it is made of a neutral compound. More preferably, 50% by weight or more thereof is composed of a trifunctional or more polyfunctional compound. Further, specific preferred polyfunctional compounds (a) are the following polyfunctional compounds having no urethane bond with acrylic urethane.

In the case of acrylic urethane, acrylic urethane which is a reaction product of pentaerythritol or polypentaerythritol which is a polymer thereof, polyisocyanate and hydroxyalkyl (meth) acrylate, or hydroxyl group-containing poly (pentaerythritol or polypentaerythritol) Acrylic urethane, which is a reaction product of (meth) acrylate and polyisocyanate, is preferably a trifunctional or more (preferably 4 to 20) compound.

As the polyfunctional compound having no urethane bond, pentaerythritol poly (meth) acrylate and isocyanurate poly (meth) acrylate are preferable. The pentaerythritol-based poly (meth) acrylate refers to pentaerythritol or polyester of polypentaerythritol and (meth) acrylic acid (preferably having a functionality of 4 to 20). Isocyanurate-based poly (meth) acrylate refers to tris (hydroxyalkyl) isocyanurate or 1 to 6 per mole thereof.
It refers to a polyester (2- to 3-functional) of (meth) acrylic acid with an adduct obtained by adding mol of caprolactone or alkylene oxide.

It is also preferable to use these preferred polyfunctional compounds in combination with other bifunctional or higher polyfunctional compounds (particularly polyhydric alcohol poly (meth) acrylate).
These preferable polyfunctional compounds are preferably at least 30% by weight, particularly preferably at least 50% by weight, based on the total polyfunctional compound (a).

As the monofunctional compound which can be used together with the compound (a), for example, a compound having one (meth) acryloyl group in the molecule is preferable. Such a monofunctional compound may have a functional group such as a hydroxyl group and an epoxy group. Preferred monofunctional compounds are (meth) acrylates, ie (meth) acrylates.

Specific examples of the monofunctional compound include the following compounds. Methyl (meth) acrylate,
Ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, glycidyl (meth) acrylate.

In order to enhance the abrasion resistance of the cured product layer which is in direct contact with the outermost layer, the coating composition (A) has an effective amount of an average particle size of 2%.
Colloidal silica of less than or equal to 00 nm can be included.
The cured product layer containing colloidal silica may be present in any of the layers of the multilayer configuration. The average particle size of the colloidal silica is 1-1.
00 nm is preferred, and 1 to 50 nm is particularly preferred. The colloidal silica is preferably the following surface-modified colloidal silica in terms of dispersion stability and improvement in adhesion to the compound (a).

When the colloidal silica is used, the amount of the colloidal silica is determined by the amount of the curable component (compound (a)) in the coating composition (A) in order to sufficiently exert its effect.
5 parts by weight or more, and preferably 10 parts by weight or more, based on 100 parts by weight of (total of monofunctional compound).

If the amount is too small, it is difficult to obtain sufficient wear resistance. If too much, the cured film becomes cloudy (haze)
Is more likely to occur. Therefore, the amount of colloidal silica in the coating composition (A) is preferably 300 parts by weight or less based on 100 parts by weight of the curable component. A more preferred amount of the colloidal silica is 50 to 250 parts by weight based on 100 parts by weight of the curable component.

As the colloidal silica, a surface-unmodified colloidal silica can be used. Preferably, a surface-modified colloidal silica (hereinafter simply referred to as a modified colloidal silica) is used. The modified colloidal silica improves the dispersion stability of the colloidal silica in the composition. It is considered that the average particle size of the colloidal silica fine particles is not substantially changed or slightly increased by the modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range. Hereinafter, the modified colloidal silica will be described.

Various dispersion media are known as the dispersion medium of colloidal silica, and the dispersion medium of the raw material colloidal silica is not particularly limited. If necessary, the modification can be performed by changing the dispersion medium, and the dispersion medium can be changed after the modification. The dispersion medium of the modified colloidal silica is preferably used as it is as the medium (solvent) of the coating composition (A).

As a medium of the coating composition (A), a solvent having a relatively low boiling point, that is, a usual solvent for a coating material is preferable from the viewpoint of drying properties and the like. The dispersion medium of the raw material colloidal silica, the dispersion medium of the modified colloidal silica and the medium of the coating composition (A) are all preferably the same medium (solvent) for reasons such as ease of production. As such a medium, an organic medium widely used as a solvent for paint is preferable.

As the dispersion medium, for example, the following dispersion medium can be used. water. Methanol, ethanol, 2-
Lower alcohols such as propanol, n-butanol, 2-methylpropanol, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol. Cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone and the like.

As described above, the dispersion medium is particularly preferably an organic dispersion medium, and among the organic dispersion mediums, alcohols and cellosolves are more preferred. Note that an integrated product of colloidal silica and a dispersion medium in which the colloidal silica is dispersed is referred to as a colloidal silica dispersion.

The modification of the colloidal silica is preferably performed using a compound having a hydrolyzable silicon group or a silicon group having a hydroxyl group bonded thereto (hereinafter, these are referred to as modifiers). It is considered that silanol groups are generated by hydrolysis of the hydrolyzable silicon groups, and these silanol groups react with and bind to silanol groups that are considered to be present on the colloidal silica surface, and the modifier binds to the colloidal silica surface. Two or more modifiers may be used in combination. Further, as described below, a reaction product obtained by previously reacting two types of modifying agents having reactive functional groups that are reactive with each other can also be used as the modifying agent.

The modifying agent may have two or more hydrolyzable silicon groups or silanol groups, a partial hydrolysis condensate of a compound having a hydrolyzable silicon group or a partial condensation of a compound having a silanol group. It may be a thing. Preferably, a compound having one hydrolyzable silicon group is used as a modifying agent (a partially hydrolyzed condensate may be generated during the modification treatment). The modifier preferably has an organic group bonded to a silicon atom, and at least one of the organic groups is preferably an organic group having a reactive functional group.

Preferred reactive functional groups are amino, mercapto, epoxy and (meth) acryloyloxy. The organic group to which the reactive functional group binds is preferably an alkylene group having 8 or less carbon atoms or a phenylene group, excluding the reactive functional group, and particularly preferably an alkylene group having 2 to 4 carbon atoms (particularly, a polymethylene group).

Specific examples of the modifying agent include the following compounds when classified according to the type of the reactive functional group. (Meth) acryloyloxy group-containing silanes; 3
-(Meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

Amino group-containing silanes; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane,
3-ureidopropyltriethoxysilane, N- (N-
Vinylbenzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Mercapto group-containing silanes; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like.

Epoxy group-containing silanes; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

Isocyanate group-containing silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, and 3-isocyanatopropylmethyldiethoxysilane.

The reaction products obtained by previously reacting two types of modifiers having reactive functional groups which are mutually reactive include, for example, a reaction product of an amino group-containing silane and an epoxy group-containing silane, Reaction products of group-containing silanes with (meth) acryloyloxy group-containing silanes, reaction products of epoxy group-containing silanes with mercapto group-containing silanes, reaction products of two molecules of mercapto group-containing silanes, etc. There is.

The modification of the colloidal silica is usually carried out by bringing a modifier having a hydrolyzable group into contact with the colloidal silica in the presence of a catalyst to effect hydrolysis. For example, it can be modified by adding a modifier to the colloidal silica dispersion and hydrolyzing the modifier in the colloidal silica dispersion.

The catalyst includes an acid and an alkali. Preferably, an acid selected from inorganic acids and organic acids is used.
As the inorganic acid, for example, hydrohalic acid such as hydrochloric acid, hydrofluoric acid and hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. As the organic acid, formic acid, acetic acid, oxalic acid, acrylic acid, methacrylic acid and the like can be used.

The reaction temperature is preferably from room temperature to the boiling point of the solvent to be used, and the reaction time depends on the temperature, but is preferably between 0.1 and 1.0.
A range from 5 to 24 hours is preferred.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but the modifiers 1 to 10 are added to 100 parts by weight of the colloidal silica (solid content in the dispersion).
0 parts by weight is suitable. If the amount of the modifier is less than 1 part by weight, it is difficult to obtain the effect of surface modification. If the amount exceeds 100 parts by weight, a large amount of unreacted modifier or hydrolyzate to condensate of the modifier not supported on the surface of the colloidal silica is generated, and these act as a chain transfer agent during curing of the coating composition. Or may act as a plasticizer for the cured product and reduce the hardness of the cured product.

In order to cure the compound (a), the coating composition (A) usually contains a photopolymerization initiator. Known or known photopolymerization initiators can be used. Particularly, commercially available products that are easily available are preferable. A plurality of photopolymerization initiators may be used in the transparent cured product layer.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-acyloxime esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.),
There are acylphosphine oxide-based photopolymerization initiators, diacylphosphine oxide-based photopolymerization initiators, and other photopolymerization initiators.

In particular, it is preferable to use an acylphosphine oxide-based photopolymerization initiator and a diacylphosphine oxide-based photopolymerization initiator. Further, the photopolymerization initiator can be used in combination with a photosensitizer such as an amine. Specific examples of the photopolymerization initiator include the following compounds.

4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 1
-(4-dodecylphenyl) -2-methylpropane-1
-One, 1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- {4
-(Methylthio) phenyl} -2-morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-
Butylperoxycarbonyl) benzophenone, 9.1
0-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-
Diethyl isophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

The amount of the photopolymerization initiator in the coating composition (A) is 0.01 to 20 parts by weight, especially 0 to 100 parts by weight of the curable component (total of the compound (a) and the monofunctional compound). 0.1 to 10 parts by weight is preferred.

The coating composition (A) may contain a solvent and various additives in addition to the above basic components. The solvent is usually an essential component, and the solvent is used unless the polyfunctional compound is a liquid having a particularly low viscosity. As the solvent, a solvent usually used for a coating composition containing the compound (a) as a curing component can be used. The dispersion medium of the raw material colloidal silica can be used as a solvent as it is. Further, it is preferable to select and use an appropriate solvent depending on the type of the inorganic plate.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the drying temperature conditions, and the like. Usually, it is used in an amount of 100 times or less, preferably 0.1 to 50 times the weight of the curable component in the composition. Examples of the solvent include solvents such as lower alcohols, ketones, ethers, and cellosolves, which are mentioned as the solvents used for the hydrolysis for modifying the colloidal silica. Other examples include esters such as n-butyl acetate and diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons, and the like.

The coating composition (A) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer, an antioxidant and a thermal polymerization inhibitor, a leveling agent, an antifoaming agent, a thickener, and an antisettling agent. , Pigments, dispersants, antistatic agents, surfactants such as antifoggants,
A curing catalyst selected from acids, alkalis and salts may be appropriately contained.

It is particularly preferable that the coating composition (A) contains an ultraviolet absorber or a light stabilizer. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, and the like which are generally used as an ultraviolet absorber for a synthetic resin are preferable. As the light stabilizer, a hindered amine-based light stabilizer (such as a 2,2,4,4-tetraalkylpiperidine derivative) which is also commonly used as a light stabilizer for a synthetic resin is also preferable.

Ultraviolet rays are particularly preferred as the active energy rays for curing such a coating composition (A). However, it is not limited to ultraviolet rays, and electron beams and other active energy rays can be used. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps,
Ultra-high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used.

The thickness of the cured product layer formed from the coating composition (A) is preferably 1 to 50 μm. When the thickness is more than 50 μm, curing by active energy rays becomes insufficient, and the adhesion to the inorganic plate is apt to be deteriorated, which is not preferable. If this layer thickness is less than 1 μm, the abrasion resistance of this layer may be insufficient, and the abrasion resistance and scratch resistance of the outermost layer on this layer may not be sufficiently exhibited. A more preferred layer thickness is 2 to 30 μm.

The curable coating composition (B) capable of forming the outermost layer of silica contains a soluble compound capable of forming silica and usually contains a solvent. Examples of the soluble compound capable of forming silica include a tetrafunctional hydrolyzable silane compound, a partially hydrolyzed condensate thereof, and polysilazane. Examples of the tetrafunctional hydrolyzable silane compound and its partially hydrolyzed condensate include tetraalkoxysilane and its partially hydrolyzed condensate. However, polysilazane is preferably used. Since polysilazane forms silica having a more dense structure, the outermost layer having more excellent surface properties can be obtained.

Examples of the polysilazane include polysilazane (perhydropolysilazane) substantially free of an organic group, polysilazane in which a hydrolyzable group such as an alkoxy group is bonded to a silicon atom, and an organic group such as an alkyl group bonded to a silicon atom. There are polysilazanes. As such a polysilazane, it is preferable that silica having substantially no organic group is formed by a hydrolysis reaction at the time of curing even if it has an organic group. In particular, perhydropolysilazane is preferable from the viewpoint of low firing temperature and denseness of a cured film after firing. The cured product obtained by sufficiently curing the polysilazane becomes silica containing almost no nitrogen atoms.

The polysilazane comprises a polymer having a chain, cyclic or crosslinked structure, or a polymer having a plurality of these structures in the molecule. The polysilazane preferably has a number average molecular weight of 200 to 50,000. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured film even when firing. On the other hand, if the number average molecular weight exceeds 50,000, it becomes difficult to dissolve in a solvent, and the coating composition (B) may become viscous.

Examples of the solvent for dissolving polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and the like.
Ethers such as alicyclic ethers can be used. Specifically, the following can be exemplified.

Hydrocarbons such as pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, methylene chloride, chloroform, Carbon tetrachloride, bromoform,
Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, and tetrachloroethane; and ethers such as ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyldioxane, tetrahydrofuran, and tetrahydropyran.

When these solvents are used, a plurality of types of solvents may be used in combination in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent to be used varies depending on the coating method to be employed, the structure of polysilazane, the average molecular weight, and the like, but it is preferable to prepare the solvent in a solid content range of 0.5 to 80% by weight.

In order to cure the polysilazane to silica, heating which is usually called calcination is required. But,
The inorganic plate, which is the base material in the present invention, usually contains organic fibers, so that the firing temperature is limited. That is, it is difficult to cure the substrate by heating it to a temperature higher than the heat resistant temperature of the substrate.

Generally, the heat resistance of the cured product of the coating composition (A) is higher than that of the substrate. However, in some cases, the heat resistance of this cured product may be lower than the heat resistance of the substrate,
In that case, it may be necessary to cure the polysilazane at a temperature lower than the heat resistant temperature of the cured product. Therefore, in the present invention, the firing temperature of polysilazane is preferably set to 200 ° C. or lower when an inorganic plate is used as a base material.

A catalyst is usually used to lower the firing temperature of polysilazane. Depending on the type and amount of the catalyst, it can be calcined at a low temperature, and in some cases, can be cured at room temperature. An atmosphere in which oxygen is present, such as in air, is preferable as the atmosphere in which the firing is performed. By firing polysilazane, its nitrogen atoms are replaced by oxygen atoms to produce silica. By firing in an atmosphere in which sufficient oxygen exists, a dense silica layer is formed.

It is preferable to use a catalyst capable of curing polysilazane at lower temperature. Such catalysts include, for example, gold, silver, palladium, platinum,
Metal catalysts composed of fine particles of a metal such as nickel (see JP-A-7-196986), amines and acids (see JP-A-9-19686)
31333). As amines, for example, monoalkylamine, dialkylamine, trialkylamine, monoarylamine, diarylamine,
And cyclic amines. Examples of the acids include organic acids such as acetic acid and inorganic acids such as hydrochloric acid.

The amount of the catalyst to be blended was polysilazane 100.
The amount is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on parts by weight. If the amount is less than 0.01 part by weight, a sufficient catalytic effect cannot be expected. If the amount is more than 10 parts by weight, aggregation of the catalysts tends to occur, which may impair transparency.

The coating composition (B) may contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer and an antioxidant, a leveling agent, an antifoaming agent, a thickener, an antisettling agent, and a pigment. Surfactants such as a dispersant and an antistatic agent may be appropriately blended and used.

The thickness of the cured product layer formed using the coating composition (B) is preferably 0.05 to 10 μm. If the thickness of the outermost layer is more than 10 μm, further improvement in surface properties such as scratch resistance cannot be expected, and the layer becomes brittle, and cracks and the like are easily generated in this layer even by slight deformation of the coated molded product. . On the other hand, if the thickness is less than 0.05 μm, the outermost layer may not sufficiently exhibit wear resistance and scratch resistance. More preferred layer thickness is 0.1 to 3 μm
m.

The two types of coating compositions (A) as described above,
As a method for forming two cured product layers formed by using (B), a usual coating method can be adopted. For example,
First, the coating composition (A) is applied and cured on the inorganic plate, and then the coating composition (B) is applied and cured on the surface of the cured product to obtain the desired coated molded plate. Can be

Means for applying these coating compositions is not particularly limited, and a known or well-known method can be employed.
For example, dip method, flow coat method, spray method,
Methods such as bar coating, gravure coating, roll coating, blade coating, air knife coating, spin coating, slit coating, and microgravure coating can be used.

After coating, if the coating composition contains a solvent, the coating composition is dried to remove the solvent, and then, in the case of a layer using the coating composition (A), the coating composition is cured by irradiation with ultraviolet rays or the like. In the case of the layer using (B), the layer is cured by heating or left at room temperature. As the combination (timing) of the curing of the coating composition (A) and the application to the curing of the coating composition (B), the following four methods can be mentioned.

1) A method of applying the coating composition (A), irradiating a sufficient amount of active energy rays to complete the curing, and then coating the coating composition (B) thereon. (Method described above).

2) After coating the coating composition (A) to form an uncured layer of the coating composition (A), apply the coating composition (B) on the uncured layer. To form a layer of the uncured material of the coating composition (B), and then irradiate a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (A). In this case, the uncured material of the coating composition (B) is cured almost simultaneously with the uncured material of the coating composition (A), or is cured by heating after curing the uncured material of the coating composition (A).

3) The minimum active energy ray (typically about 30
(Irradiation amount up to 0 mJ / cm ² ) to form a partially cured layer of the coating composition (A), and then coat the coating composition (B) on the partially cured layer. A method of forming an uncured layer of the coating composition (B) and thereafter irradiating a sufficient amount of active energy rays to terminate the curing of the partially cured product of the coating composition (A). The curing of the uncured material of the coating composition (B) is the same as in the above 2).

4) After forming an uncured or partially cured layer of the coating composition (A) and an uncured layer of the coating composition (B) as described in 2) or 3) above, The uncured material of the composition (B) is partially or completely cured first, and then the uncured or partially cured material of the coating composition (A) is completely cured. In this case, at the time of curing the uncured material of the coating composition (B), the coating composition (A) is preferably a partially cured material rather than an uncured material.

In order to increase the adhesion between the two cured product layers, the above method 2) or 3) is more preferable. However, in the case of the method 2), when a dipping method is used as a method of applying the coating composition (B), the component of the uncured material of the coating composition (A) is replaced with the dipping liquid of the coating composition (B). Due to the possibility of contamination, there is a restriction that coating by such a dipping method is not suitable.

[0103]

EXAMPLES The present invention will be described below with reference to Reference Examples (Examples 1 and 2), Examples (Examples 3 to 8), and Comparative Examples (Examples 9 to 13), but the present invention is not limited thereto. The measurement and evaluation of various physical properties were performed by the following methods, and the results are shown in Table 1.

[Abrasion resistance] According to the surface wear test method in JIS-A1453, 5 was measured using a Taber type wear tester.
The change in weight when 500 rotations were performed with a load of 30 g was measured (average value of three times).

[Weather Resistance] Using a super UV tester, a black panel temperature of 63 ° C. was irradiated with ultraviolet rays for 6 hours, then the temperature was lowered and the cycle of dew condensation was repeated for 2 hours. Evaluated by the difference from the initial.

[Freeze-thaw resistance] According to the freeze-thaw test method in ASTM-C-666, -17.8 ° C to +4.4.
The volume expansion coefficient after repeating the cycle at 100 ° C. 100 times was measured.

Example 1 (Preparation of Inorganic Plate) Cement 2
8.6% by weight, slag 46.7% by weight, silica fine powder 7.
To 6% by weight, 9.5% by weight of pearlite, and 7.6% by weight of pulp, 300 to 400% by weight of water was added and mixed. The obtained slurry was formed into a plate-like body (150 mm
× 300 mm, thickness 10 mm). This molded body was cured in saturated steam at 80 ° C. for 15 hours.
The molded body was dried at 0 ° C. so that the moisture content of the molded body became 7%. This inorganic plate was used as a substrate in the following examples. The measurement was also performed on this inorganic plate.

Example 2 (Preparation of Modified Colloidal Silica Dispersion) 100 parts by weight of ethyl cellosolve-dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm), 5 parts by weight of 3-mercaptopropyltrimethoxysilane And 3.0 parts by weight of 0.1N hydrochloric acid.
After heating and stirring for 12 hours, the mixture was aged at room temperature for 12 hours to obtain a mercaptosilane-modified colloidal silica dispersion.

[Example 3] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, add 2-propanol 15
g, butyl acetate 15 g, ethyl cellosolve 7.5 g,
2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2- {2-hydroxy-5-
1000 mg of (2-acryloyloxyethyl) phenyl} benzotriazole and 200 mg of bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate are added and dissolved, and then dipenta having a hydroxyl group is added. 10.0 g of urethane acrylate (containing an average of 15 acryloyl groups per molecule), which is a reaction product of erythritol polyacrylate and partially nullated hexamethylene diisocyanate, is added, and the mixture is stirred at room temperature for 1 hour to form a coating composition (hereinafter referred to as “coating composition”). , Coating liquid 1).

The coating liquid 1 was applied to the inorganic plate of Example 1 using a bar coater (wet thickness: 30 μm) and was kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 3000 mJ / cm ² (wavelength 3
Ultraviolet light having a UV energy in the range of 00 to 390 nm (the same applies hereinafter) was applied to form a transparent cured product layer having a thickness of 10 μm.

Next, a xylene solution of perhydropolysilazane (solid content: 20% by weight, trade name: L110, manufactured by Tonen Co.) (hereinafter referred to as coating liquid 2) (which is hereinafter referred to as coating liquid 2) was further coated thereon using a bar coater. (Wet thickness 6μm)
The outermost layer was sufficiently cured by holding in a hot air circulating oven at 80 ° C. for 10 minutes and then in a hot air circulating oven at 100 ° C. for 120 minutes. And it was confirmed by IR analysis that the outermost layer was a complete silica coating. Thus, a transparent cured product layer having a total thickness of 11.2 μm was formed on the inorganic plate. The measurement was performed using this sample.

[Example 4] The sample preparation method in Example 3 was changed as follows. After applying the coating liquid 1, the coating liquid was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and irradiated with ultraviolet rays of 150 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere to obtain a partially cured product having a thickness of 10 μm. A layer was formed. Next, the coating liquid 2 was coated thereon using a bar coater (wet thickness: 6 μm), and kept in a hot air circulating oven at 80 ° C. for 10 minutes. An ultraviolet ray of 3000 mJ / cm ² was irradiated. Then, it was kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 5] The sample preparation method in Example 4 was changed as follows. Instead of being kept in a hot air circulating oven at 100 ° C. for 120 minutes, it was cured at room temperature for one day. The measurement was performed using this sample.

Example 6 The sample preparation method in Example 3 was changed as follows. After the coating liquid 1 was coated, the coating liquid 1 was kept in a hot air circulating oven at 80 ° C. for 5 minutes, and then the coating liquid 2 was coated thereon using a bar coater (wet thickness 6 μm).
m) and kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then placed in an air atmosphere using a high-pressure mercury lamp for 30 minutes.
It was irradiated with ultraviolet rays of 00 mJ / cm ² and kept in a hot air circulating oven at 100 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 7] 1 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, add 2-propanol 15
g, butyl acetate 15 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 150 mg, 2-
1000 mg of {2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole and 200 mg of bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate were added and dissolved. Subsequently, 10.0 g of tris (2-acryloyloxyethyl) isocyanurate was added, and the mixture was stirred at room temperature for 1 hour. Subsequently, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 2 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 3).

The coating liquid 3 was applied to the inorganic plate of Example 1 using a bar coater (wet thickness: 30 μm), and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with 150 mJ / cm ² ultraviolet rays using a high-pressure mercury lamp in an air atmosphere to form a 10 μm-thick partially cured product layer. Then, the coating liquid 2 was coated thereon using a bar coater (wet thickness: 6 μm), kept in a hot air circulating oven at 80 ° C. for 10 minutes, and then 3,000 mJ in an air atmosphere using a high-pressure mercury lamp. / Cm ² UV light,
It was kept in a hot air circulating oven at 0 ° C. for 120 minutes. The measurement was performed using this sample.

[Example 8] The sample preparation method in Example 7 was changed as follows. Instead of being kept in a hot air circulating oven at 100 ° C. for 120 minutes, it was cured at room temperature for one day. The measurement was performed using this sample.

Example 9 The coating liquid 1 was applied to the inorganic plate of Example 1 using a bar coater (wet thickness: 20 μm), and
It was kept in a hot air circulating oven at 0 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 3000 mJ / cm ²
Was irradiated to form a transparent cured product layer having a thickness of 6 μm. The measurement was performed using this sample.

[Example 10] The coating liquid 2 was applied to the inorganic plate of Example 1 using a bar coater (wet thickness 30 µm).
It was kept in a hot air circulating oven at 80 ° C. for 10 minutes. Subsequently, it is kept in a hot air circulation oven at 100 ° C. for 120 minutes,
A transparent cured product layer having a thickness of 6 μm was formed. The measurement was performed using this sample.

[Example 11] The coating liquid 3 was applied to the inorganic plate of Example 1 using a bar coater (wet thickness: 20 µm).
It was kept in a hot air circulating oven at 80 ° C. for 5 minutes. Then, in an air atmosphere, using a high-pressure mercury lamp, 3000 mJ / cm
By irradiating ultraviolet rays of No. ² , a transparent cured product layer having a thickness of 6 μm was formed. The measurement was performed using this sample.

[Example 12] An acrylic sealing paint (trade name, manufactured by Dainippon Paint Co., Ltd.) was applied to the inorganic plate of Example 1 using a bar coater.
AG107) (wet thickness 20 μm) and 9
It was kept in a hot air circulating oven at 0 ° C. for 10 minutes. next,
Using a bar coater, moisture-proof paint (trade name of Dainippon Paint Co., Ltd .:
AG207) (wet thickness: 20 μm) to give 9
It was kept in a hot air circulating oven at 0 ° C. for 10 minutes. Further, an acrylic paint (trade name: AG301, manufactured by Dainippon Paint Co., Ltd.) was applied using a bar coater (wet thickness: 10 μm), and was kept in a hot-air circulation oven at 90 ° C. for 10 minutes.
The measurement was performed using this sample.

[Example 13] The sample preparation method in Example 12 was changed as follows. 8 (wet thickness: 6 μm) using coating liquid 2 instead of acrylic paint
Hold in a hot air circulating oven at 0 ° C. for 10 minutes, then
It was kept in a hot air circulating oven at 00 ° C. for 120 minutes. The measurement was performed using this sample.

[0123]

[Table 1]

[0124]

The coated molded plate of the present invention is an inorganic building material excellent in abrasion resistance, weather resistance and freeze-thaw resistance.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09D 183/16 C09D 183/16 (72) Inventor Hiroshi Yamamoto 1150 Hazawacho, Kanagawa-ku, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd. (72) Inventor Seiji Inoue 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture Inside Asahi Glass Co., Ltd.

Claims (5)

[Claims] 1. A coated molded plate comprising an inorganic plate and at least two hardened material layers provided on at least a part of the surface of the inorganic plate, wherein the inner layer in contact with the outermost layer of the two or more hardened material layers has the following coating: A coated molded plate, which is a layer of a cured product of the composition (A), wherein the outermost layer is a layer of a cured product of the following coating composition (B). Coating composition (A): An active energy ray-curable coating composition containing a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups. Coating composition (B): a curable coating composition capable of forming silica. 2. The coating composition (A) further comprises an average particle size of 20
The coated molded plate according to claim 1, comprising colloidal silica having a particle size of 0 nm or less. 3. The coated molded plate according to claim 1, wherein the coating composition (B) is a coating composition containing polysilazane. 4. A method for producing a coated molded plate according to claim 1, wherein the coating composition (A) is applied to the surface of the inorganic plate.
A method for producing a coated molded plate, comprising: forming an uncured material layer of the coating composition (B) on the surface of the cured material layer after forming the cured material layer of the above (1). 5. The method for producing a coated molded plate according to claim 1, wherein the coating composition (A) is applied to the surface of the inorganic plate.
After forming a layer of an uncured or partially cured product, a coating composition (B) is formed on the surface of the layer of the uncured or partially cured product.
Forming an uncured material layer of the coating composition (A), and thereafter curing the uncured or partially cured material of the coating composition (A) and the uncured material of the coating composition (B). Method.